JPS6148703B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method of protecting photographic images, and more particularly to a method of protecting a photographic layer by bonding a cover sheet to the photographic layer. Storing and using photographic images as records without undergoing any changes over many years is a major challenge facing photographic technology. Many inventions have been made for this purpose and great progress has been made, but it is still not enough. It is well known that a large part of the instability of current photographic images comes from storing photographic prints in the presence of oxygen. In other words, silver images, especially in the presence of silver complexing agents, are oxidized to silver salts even in the dark, resulting in a decrease in image density, and dye images, especially in the presence of oxygen, are oxidized to silver when exposed to light. Destroyed. Attempts have already been made to protect photographic images by blocking oxygen. For example, JP-A-49
-11,330 and 50-57,223 have 2.0cc/ ^m2・
A method for enclosing photographic prints with oxygen permeability below HR/ATM (20°C), and furthermore,
No. 11,235 discloses a specific photographic film unit using a composite support consisting of a polyvinyl alcohol film and a cellulose acetate film on both sides. However, the implementation of the previously known oxygen barrier protection methods has been hampered by insufficient oxygen barrier, poor workability, relatively high cost, and poor image quality due to unsuitable optical properties when printing. ,
The prints were not completely satisfactory due to the poor handling of the prints due to the protected form of the photographic prints, and the discoloration of the oxygen-blocking substance over time. Additionally, oxygen barrier film materials developed in areas other than photography cannot be used as they are for the unique purpose of protecting photographic prints due to unsuitable optical properties and long-term instability of the materials themselves. It was difficult to use. The first object of the present invention is to effectively protect photographic prints using a novel cover sheet that strongly suppresses the penetration of oxygen from the photographic layer side into prints having a photographic layer containing a photographic image on a support. The purpose is to provide a method. A second object of the present invention is to provide an easy-to-implement print protection method that can uniformly and firmly fix a cover sheet to a photographic print by a simple operation. A third object of the invention is to provide a method of providing protected photographic prints that is optically and mechanically easy to handle and store. Other objects of the invention will become apparent from the detailed description below. The object of the present invention is to provide at least (1) a transparent layer made of a saponified ethylene-vinyl acetate copolymer and (2) an outermost layer on the surface of a print having a photographic image layer on a support. A cover sheet having a layer that forms a transparent adhesive layer that uniformly and firmly adheres the cover sheet to the image layer of the print (including the protective layer coated on the image layer; the same applies hereinafter) is inserted through the adhesive layer. It has been found that this can be achieved by bonding them together. Ethylene, the oxygen barrier material used in the present invention
The hydrolyzed (saponified) product of vinyl acetate copolymer is represented by the general formula. Here, on a molar basis, x is from 0.2 to 0.7, y is from 0.25 to 0.8, and z is 0.1 or less. A copolymer having such a composition can be obtained by saponifying an ethylene-vinyl acetate copolymer of the general formula. Here, on a molar basis, x is from 0.2 to 0.7 and y+z is from 0.3 to 0.8. A polymer of the general formula can be obtained by saponifying 90% or more of the acetyloxy groups of the polymer of the general formula. Particularly preferably x is from 0.26 to 0.45, y
is from 0.5 to 0.74. The degree of saponification is preferably 96% or more. A high rate of saponification from a general formula to a general formula is explained by Hiroshi Iwasaki and Kiyoshi Yonezu, “Alkali saponification reaction of ethylene-vinyl acetate copolymer resin” Kobunshi Ronshu Vol. 35, No. 1, pp. 33-39. (1978)). The present invention can also be achieved by treating at least one side of a pre-formed ethylene-vinyl acetate membrane with a strong alkaline solution. The membrane of saponified ethylene-vinyl acetate used in the present invention is from about 1 micron to about 100 microns when placed on a separate support, preferably from about 3 microns to about 40 microns, and used as a standalone polymer membrane. Advantageously, the polymer film has a thickness of from about 5 microns to about 200 microns, preferably from about 10 microns to about 80 microns. When placed on another support, the melt may be cast directly onto the support, the solution may be applied directly onto the support, or the membrane may be formed separately as a single film. The highly saponified ethylene/vinyl acetate copolymer used in the present invention can be used as an oxygen barrier material for protecting photographic prints. It has a greater oxygen blocking ability than polyvinyl alcohol, saran, nylon, etc., which was previously used, and it maintains a high oxygen blocking ability even under fairly high humidity, making it necessary to coat the surface with a hydrophobic polymer layer to prevent moisture. The adhesive layer used in the present invention is particularly suitable for protecting prints because it is stable and does not stain even under harsh conditions. It adheres uniformly to the print surface and the cover sheet, and has an adhesive strength of about 100 g or more, preferably about 200 g or more per 1 cm of bonded width.One of the print/cover sheets with such adhesive strength
The integrated laminate is less prone to peeling at its edges, and the cover sheet only needs to be coextensive with the print to achieve its protective purpose. Various types of adhesives can be used in the present invention, among which preferred types include the following. (1) Solvent-activated type (especially rewetting type): A polymer solution containing a solvent (boiling point at normal pressure of 200°C or lower, preferably 150°C or lower) that evaporates after the cover sheet and print come into contact. A polymer layer swollen with a suitable solvent is interposed between the print and the cover sheet. A method of supplying a solvent to the outermost polymer layer of the cover sheet before contact with the print, and a method of adhering the cover sheet to the solvent contained in the image layer of the print (e.g. water remaining after processing) before contact with the cover sheet. There are methods of making the agent act on the polymer layer. The adhesive layer suitable for using water as a solvent and located at the outermost layer of the cover sheet includes (a) a weakly hardened gelatin layer, (b) a weakly hardened gelatin derivative layer, and (c) a weakly hardened gelatin layer. (d) a weakly hardened layer comprising a mixture of gelatin partially modified by an acylation reaction such as phthalylation and a hydrophilic polymer such as a partial hydrolyzate of polyvinyl acetate; Weakly crosslinked layers of polymers containing carboxyl groups, such as polyacrylic acid or CMC, partially hydrophilic polymers containing (e)carboxyl groups, such as n-butyl copolymers of methyl vinyl ether and maleic anhydride. There are half-esterification products with alcohol and copolymers of acrylic acid and butyl acrylate. In addition, layers of starch, casein, dextrin, polyvinyl alcohol, partially saponified polyvinyl acetate, polyethylene oxide, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, hydroxyethylcellulose, methylcellulose, etc. can also be used. The dura of gelatin contains aldehydes such as formaldehyde and mucochloric acid,
Active halogen compounds such as 2-hydroxy-4,6-dichloro-s-triazine salts, compounds with two or more vinyl sulfonyl groups or vinyl carbonyl groups, etc. are used for crosslinking polymers with carboxy groups. Particularly suitable are compounds having two or more chromate or epoxy groups, such as vane. In order to weakly crosslink or harden these hydrophilic polymers, it is appropriate to use 0.005 part to 1.0 part per 1 part by weight of the polymer. The cover sheet mentioned above is 0.5
It is suitable to have a film thickness of from 1 micron to 20 microns, preferably from 1 micron to 10 microns. (2) Adhesive type (pressure-sensitive adhesive type): It is provided as a layer on one side of the cover sheet and is pressed onto the surface of the photographic print. Before use, the surface of the adhesive layer is
Advantageously, the release layer is covered with a release material having a layer of silicone resin or the like, which can be provided on the back side of the cover sheet or on a separate sheet of paper or the like. The adhesive can be easily selected from conventionally known adhesives, such as those described in Keiji Fukuzawa's ``Adhesive Technology'' (Kobunshi Publishing Co., Ltd.), according to the criteria of the intended use. For example, EVA (ethylene/vinyl acetate copolymer)
rubber-based hot melt adhesives such as SBR, rubber-based resins such as SBR, ABR, neoprene, polyisoprene, butyl rubber, chloride rubber, polyacrylic esters, polyvinyl acetate, polyvinyl butyral, polybenyl ether, etc. A resin-based solution adhesive is suitable. These polymers are applied to the cover sheet in the form of a melt, solution or latex. (3) Heat-seal type (heat-sensitive adhesive type): A layer is provided on one side of the cover sheet, and it is pressed and adhered to the surface of the photographic print under the action of heat.
In order to carry out the present invention, this mold has the practical advantages of being able to quickly form a bond simply by heating, leaving few air bubbles on the printed surface, and being able to form a strong bond, and the bonding strength improving over time. It is particularly suitable because of the durability advantage of a protected print unit and is less prone to deterioration. As base polymers, (a) modified polymers similar to ethylene/vinyl acetate copolymer (EVA), (b)
Modified polymers of the same type as ethylene/acrylic acid ester copolymers (EEA, EIBA) - especially ionomer resins known as "Surlyn A" (manufactured by Mitsui Polychemical Co., Ltd.), (c) polyamide resins - especially nylon 12 (d) amorphous flexible polyester resin, and (v) polyvinyl acetate-based or polyvinylidene chloride-based resin. In addition to the base polymer, it is effective to blend tackifier components such as rosin and terpene-based resins and a plasticizer selected from high-boiling point solvents in order to facilitate the thermal bonding operation. These components are melt extruded and cast, or applied as a solution in an organic solvent or dispersed in a latex to form the outermost layer of the cover sheet. The formation of these hot-melt adhesive layers can be done using existing techniques (for example, Hiroshi Fukada, “Practical Hot Melt Adhesion”, Kobunshi Publishing Co., Ltd., 1979).
year). It is advantageous for this type of adhesive layer to contain an oil-soluble antioxidant in order to strengthen the prevention of image deterioration in the print. A particularly effective inhibitor is 2,2'-ethylene-bis-(4
-Methyl-6-tert-butylphenol), high molecular weight hindered phenol (manufactured by Ciba-Geigy)
Hindered phenols such as Irganox1076),
6-hydroxychromans as described in U.S. Pat. No. 3,432,300 and U.S. Pat. No. 3,573,052; metal complexes such as nickel dibutyl dithiocarbamate; Thiol, thione compounds such as benzimidazole and 4-methyl-4-hydroxymethyl-1-phenyl-3
-There are cyclic hydrazides such as pyrazolidinone. Desirably, the hot melt adhesive layer softens at an effective temperature of between about 40°C and 150°C, preferably between 50°C and 120°C. Adhesive layer is from 0.1 micron to 80 micron,
Preferably, it is suitable to have a film thickness between 0.5 microns and about 40 microns. (4) Reactive type: This type is placed between the cover sheet and the photographic print, and the liquid that wets both sides becomes non-fluid through a condensation or polymerization reaction to form an adhesive layer. A combination of a polyvalent carboxylic acid or a polyvalent amine and a polyvalent epoxy compound is used, and an example of a combination of a polyvalent carboxylic acid or a polyvalent epoxy compound is an alkyl-2-cyanoacrylate. In addition to the oxygen-blocking polymer layer and the adhesive layer, the image protection sheet used in the present invention may advantageously have a polymer layer to impart mechanical strength to the sheet. This strength-imparting polymer layer includes highly transparent and dimensionally stable polymers conventionally used or proposed for use in photographic supports, such as cellulose acetate, polycarbonate, polyester, and polystyrene. Polyester-based polymers are particularly suitable for their mechanical strength, solvent resistance, and heat resistance during the manufacture of the cover sheet, and for their mechanical strength during the bonding of the cover sheet and the print. It is suitable for the present invention because of its mechanical strength, water resistance, and optical properties in storage and use of print units. Among polyesters, those derived from ethylene glycol and terephthalic acid are generally advantageous, but when the adhesive layer is of a solution type using water as a solvent, US Pat. −45493, and
The moisture permeability is 10 as described in No. 54-50705.
Polyester layers larger than g/m ² 24hr0.0mm (40°C) are particularly suitable. Such a cover sheet, which has a moisture-permeable polyester support, an oxygen barrier layer and an adhesive layer, can be easily attached to the print of the photosensitive material using water, and is then incorporated in a short period of time. The water permeates through the support, oxygen barrier layer and adhesive layer, evaporates and dries.
The feature is that a protected print unit can be easily produced. The polyester film is preferably biaxially stretched. The light fastness of the image can be further improved by containing an ultraviolet absorber in one or more of the oxygen-blocking polymer layer, adhesive layer, strength-imparting polymer layer, etc. that constitute the cover sheet used in the present invention. can. The ultraviolet absorbers used in the present invention include benzotriazole compounds substituted with aryl groups (for example, those described in U.S. Pat. No. 3,533,794) and 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681). ),
Benzophenone compounds (for example, JP-A-46-2784)
), cinnamate ester compounds (e.g., those described in U.S. Pat.
4,045,229) or benzoxyzole compounds (for example, those described in U.S. Pat. No. 3,700,455), U.S. Pat.
The compound described in No. 48535, and the compound with two ultraviolet absorbing groups
Compounds with more than one compound (e.g. U.S. Pat. No. 3,936,418
No. 3936418, No. 3936305, No. 3981884,
Same No. 4001148, No. 4024153, No. 4029670, Same No.
4041011, 4070339, 4065427, 4041011, 4070339, 4065427,
No. 4085089, No. 4075220, No. 4073745, No. 4073745, No. 4075220, No. 4073745, No.
No. 4116929, No. 4105631, No. 4128559, JP-A-Sho
Examples include bis-type and tris-type ultraviolet absorbers described in No. 51-63845, No. 51-63846, and No. 51-36240. The method for protecting photographic prints of the present invention has features not found in previously known methods. First, it has a high oxygen blocking ability, and the deterioration of photographic images stored in the air is significantly suppressed. Second
In addition to being stabilized by oxygen exclusion, print units made in accordance with the present invention also stabilize images by
It can protect against the action of moisture, contamination by coloring components, contamination by oils and fats such as fingerprints, the action of microorganisms such as mold, mechanical damage, and damage by insects. Third, the image protection effect according to the present invention is less affected by the surrounding environment, especially humidity, and is maintained at a high level. Fourth, the cover sheet used in the present invention can be limited to a small thickness, resulting in less light loss during image utilization. The Dmin. of the white background of protected reflective prints can also be kept low. The protected print unit is also thin and easy to handle. Fifth, the cover sheets can be joined easily and reliably, and there is no need to create edges of the protective sheet at the printed edges. Sixth, the invention can be implemented using small amounts of inexpensive materials. Seventhly, by scattering the reflected light by using a surface finish such as a fine-grained surface, it is easy to expand the angle at which the reflected light can be observed. Photographic prints that can be protected by the present invention span photographic images made by various photographic methods and made of various materials. Photographic images well suited to be protected include silver images and dye images. Silver images are formed by chemical development, physical development, etc., and silver coexists with minute silver particles created by dissolution physical development, etc., and silver complexing agents such as thiosulfates and thiocyanates. The image made of particles turns into a silver salt under the action of oxygen and the image deteriorates.
Dye images are formed primarily as a result of the development of photosensitive silver salts (1) from couplers in combination with primary amino developers in color development methods and (2) from couplers in combination with primary amino developers in silver dye bleaching methods. From azo dyes, (3)
It is formed from a dye developer in a color diffusion transfer method, (4) from a dye-releasing redox compound in a color diffusion transfer method, and (5) from a dye transferred in a dye transfer method. In addition, dye images can also be formed by electrolytic methods, electrophotographic methods, thermal transfer methods, inkjet methods, and the like. Although these pigment images differ in degree,
Fading. In particular, fading is significantly accelerated when exposed to light in the presence of oxygen. Photographic prints that can be protected by the present invention may be reflective prints such as color paper or transmissive prints such as color transparency. These photographic prints contain an image on a support in a photographic layer consisting primarily of hydrophilic colloids, such as gelatin. The support is a rigid body such as glass, metal, or plastic, or a flexible body such as a sheet of paper, cellulose ester (e.g., cellulose nitrate, cellulose acetate), polycarbonate, polyester, etc.
Depending on the purpose, it may be transparent, light reflective, or light absorbing, and may be a single film or a composite film. For the practice of the present invention, it is desirable that the photographic print support has an oxygen permeability of 2.0 ml/m ² hr atm (20° C., dry state) or less. For example about
Polyester film with a thickness of 80 microns or more,
Glass plate, metal plate, or JP-A-11330
No. 50-57223, a support made of a composite membrane described in JP-A No. 50-57223, and also co-filed Japanese Patent Application No. 1983-
Photographic prints having a composite support having a highly saponified ethylene-vinyl acetate copolymer as an oxygen barrier layer as described in Nos. 163169 and 54-163722 may be protected according to the present invention. is highly stabilized. Photographic prints protected by this invention include:
In addition to deterioration of the image material, substances contained in the white part of the print, such as couplers, redox compounds,
Stain buildup caused by oxidative discoloration of such as fluorescent brighteners and processing solution components is prevented. The adhesive surface of the photographic print protected by the present invention is in good contact with the adhesive layer of the cover sheet;
Easy wettability is preferred for obtaining high adhesive strength. When the adhesive layer is of the hot melt type, the surface layer of the photographic print preferably contains lipophilic polymer particles, such as latex particles of poly-n-butyl acrylate, in a matrix of hydrophilic colloids. Materials used in various prints of the present invention, such as binders forming hydrophilic colloid layers and mordant layers, negative or autopositive silver halide emulsions,
Heat-developable emulsions and silver supplies, color (cyan, magenta and yellow) couplers, diffusible dye-leaving couplers (so-called DDR couplers), dye-leaving redox compounds (so-called DRR compounds), dye developers, silver dyes. Image-forming dyes for bleaching, solvents for dispersing coloring materials, emulsifiers, and other additives added to photosensitive materials or image-forming layers (e.g., sensitizing dyes, stabilizers, anti-fading agents, ultraviolet absorbers,
Hardeners, color mixing inhibitors, acid polymers, fluorescent brighteners,
Regarding internal developing agents with built-in sensitizers, coating aids, thickeners, etc.), see Research Disclosure vol.176 P.22-31
(December 1978) can be referred to. When the photographic print used in the present invention is obtained from a silver halide light-sensitive material, the developing method includes a tank development method in which the photographic print is processed by buffing in a developer, and a viscous processing solution containing a developing agent etc. is applied to the light-sensitive material. A viscous development method in which the photosensitive material is developed using a heat panel,
There is a thermal development method in which development is performed by heating with infrared rays or high frequency waves. Color developers, black and white developers, bleaching agents, fixing agents (silver halide solvents),
Image stabilizers and other processing solution additives (e.g. preservatives, solubilizing agents, toning agents, development accelerators, surfactants, alkali agents, pH buffers, anti-gabbing agents,
Antifoaming agents, water softeners, hardening agents, viscosity imparting agents, bleaching accelerators, etc.)
The description in Disclosure vol.176 P.22-31 (December 1978) can be referred to. Preferred embodiments of the present invention are shown below, but the scope of the present invention is not limited thereto. (1) In the claims, the cover sheet has a support layer. (2) In the claims and embodiment (1), the saponified product of ethylene-vinyl acetate copolymer has an ethylene content of 20 to 70 mol% and a saponification degree of 90%.
That's all. (3) In the claims and embodiments (1) and (2),
The adhesive layer is shown on pages 6 to 10 of the text. (4) In embodiment (1), each layer of the cover sheet is
support layer, ethylene-vinyl acetate copolymer layer,
The adhesive layers are arranged in this order. (5) In embodiment (1), each layer of the cover sheet is arranged in the following order: ethylene-vinyl acetate copolymer layer, support layer, and adhesive layer. (6) In embodiments (1), (4), and (5), the support layer is
Made of polyester. (7) In (6), the support layer is made of polyethylene terephthalate. (8) In the claims and (1) to (7), at least one of each layer of the cover sheet contains an ultraviolet absorber. (9) In the claims and (1) to (8), the print support is transparent. (10) In the claims and (1) to (8), the print support is white and opaque. (11) In the claims and (1) to (8), the oxygen permeability of the printing support is 2.0cc/m ² hr.
It is below ATM. (12) In (11), the print support includes a layer made of a saponified ethylene-vinyl acetate copolymer (ethylene content 20 to 70 mol%, degree of saponification 90% or more). (13) In (11), the print support consists of two or more layers, and at least one layer has an oxygen permeability.
It is less than 2.0cc/m ²・hr・atm. (14) In (13), at least one layer of the print support is a layer made of saponified ethylene-vinyl acetate copolymer (ethylene content 20 to 70 mol%, degree of saponification 90% or more). . (15) In (13), at least one layer of the print support is a layer made of polyvinyl alcohol. (16) In (13) to (15), one layer of the print support is a layer made of polyethylene terephthalate. (17) In (13) to (15), one layer of the print support is a layer made of cellulose triacetate. (18) In (13) to (15), one layer of the print support is paper. (19) In claims and (1) to (18), the photographic image of the print consists of a developed silver image. (20) In claims and (1) to (18), the photographic image of the print consists of a dye image produced by the reaction of an oxidized aromatic primary amine developer and a color-forming coupler. (21) In claims (1) to (18), the photographic image of the print is transferred by a color diffusion transfer method,
Consists of a dye image formed from a dye developer. (22) In claims and (1) to (18), the photographic image of the print consists of a dye image formed from a dye-releasing redox compound in a color diffusion transfer process. (23) In claims and (1) to (18), the photographic image of the print consists of a dye image formed in a silver-dye bleaching process. (24) In claims and (1) to (18), the photographic image of the print consists of a dye image formed by a dye transfer method. (25) In claims and (1) to (18), the photographic image of the print consists of a dye image formed by an inkjet method. Type of cover sheet used in the examples In the general formula (), x = 0.30, y =
Surlyn A (ethylene/acrylic acid-ester copolymer) was melt-extruded onto a 20-micron-thick film made by melt-extruding a polymer with the following composition: 0.66, z=0.04. A composite film sheet obtained by coating to a thickness of 40 microns. In the general formula (), x=
0.30, y = 0.66, z = 0.04 on a composite film obtained by casting the polymer to a thickness of 15 microns using a melt extrusion method.
A composite film sheet obtained by casting the Surlyn A layer to a thickness of 20 microns in the same manner as described above. Instead of the Surlyn A layer, a 7% by weight gelatin aqueous solution containing formaldehyde (gelatin
A composite film sheet obtained by coating 100 parts of formaldehyde (containing 10 parts of formaldehyde) using a dip method to a dry thickness of 6 microns. Instead of the Surlyn A layer, 2 g/ ^m2 of acrylic adhesive (2-ethylhexyl acrylate/vinyl acetate = 80/20) was applied using gravure coating, and the product was rolled up with release paper in between. Pressure bonding type composite film. Example 1 Protection of a transparent color positive made by color development method: A 15 micron thick ethylene/vinyl alcohol/vinyl acetate copolymer (molar A color photosensitive material was prepared by sequentially providing an oxygen barrier layer having a ratio of 70:29.5:0.5 and the following photographic layers on the surface. 1st layer: Red-sensitive silver iodobromide (iodine 3 mol%) emulsion 1.5 gAg/m ² , cyan coupler 0.8 g/m ² , G-
n-butyl phthalate 0.4g/ ^m2 and gelatin 3g/m2
Red-sensitive layer containing m ² , 2nd layer: 0.2 g/m ² of 2,5-di-tert-octylhydroquinone, 1 g/m ² of ultraviolet absorber, G-n
-Butyl phthalate 0.5g/ ^m2 and gelatin 1.2g/ ^m2
3rd layer: green-sensitive silver iodobromide (iodine 3 mol%) emulsion 1.5 gAg/m ² , magenta coupler 0.4 g/m ² ,
2,5-di-tert-octylhydroquinone 0.1
g/m ² , anti-fade agent 0.2 g/m ² , green-sensitive layer containing tri-o-cresyl phosphate 0.4 g/m ² and gelatin 3 g/m ² , 4th layer: yellow silver colloid 0.8 g/m ² , 2,5-
Di-tert-octylhydroquinone 0.2g/m ² , di-n-butyl phthalate 0.1g/m ² and gelatin 1.5
yellow filter layer containing g/ ^m2 , 5th layer: blue-sensitive silver iodobromide (iodine 4.5 mol%)
Emulsion 0.8gAg/m ² , Yellow coupler 0.6g/m ² ,
D-n-butyl phthalate 0.3g/ ^m2 and gelatin
Blue sensitive layer containing 2.5g/ ^m2 and 6th layer: latex of butyl acrylate 0.5
g/m ² and a layer containing 1.0 g/m ² of gelatin. These gelatin contents were hardened with 2,4-dichloro-6-hydroxy-s-triazine sodium salt. The couplers used here were as follows: The anti-fade agents used in the third layer were as follows: This light-sensitive material was exposed to light through a color positive and then subjected to the following processing to obtain a multicolored transparent color positive. Processing process Temperature Time First development 38℃ 1 minute 30 seconds Stop 〃 45 seconds Wash with water 〃 3 minutes Color reversal development 〃 2 minutes 45 seconds Wash with water 〃 45 seconds Bleach fixing 〃 3 minutes Wash with water 〃 1 minute 30 seconds Used The formulation of the treatment liquid is as follows. First developer Sodium sulfite 40g Sodium carbonate 16g Sodium bicarbonate 7g Sodium thiocyanate 1g Potassium bromide 1.5g Potassium iodide 6mg Hydroquinone 7g Phenidone 0.4g Add water 1 Stop solution Glacial acetic acid 20g Sodium hydroxide 1.5g Add water 1 Color developer Benzyl alcohol 17ml Ethylene glycol 2ml 4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-m-toluidine 2/
Trisulfate monohydrate 4.5g Sodium sulfite 2.5g Sodium carbonate 30g Sodium hydroxide 2.5g Hydroxylamine 2.5g Add water 1 Bleach-fix solution Ethylenediamine-4-ferric ammonium acetate monohydrate 100g Ethylenediamine-tetraacetic acid disodium 4g Aqueous ammonia (28%) 20ml Ammonium thiosulfate 200g Thiourea 2g Add water 1 The image layer side of the transparent positive A thus obtained was brought into close contact with the adhesive layer side of the composite film sheet, and heated to 110°C. A laminate transparency-B was obtained by passing between two pressure rollers. In the same manner, a transparent positive C-C was obtained by laminating a composite film sheet. Transparent positive - After wetting the image layer side of A and the adhesive layer side of the composite film sheet with water, both layers are brought into close contact with each other, passed between two pressure rollers, and dried to produce a laminated transparent positive. I got a D. After peeling off the release paper from the composite film sheet,
This adhesive layer side and the image layer side of the transparent positive A were brought into close contact and passed between two pressure rollers to obtain a laminated transparent positive E. Samples -A to -E were irradiated with light for 40 days using a light irradiation tester (illuminance 20,000 lux) equipped with a xenon arc lamp, and changes in color tone before and after light irradiation were examined. Although a significant change in color tone was observed in Sample-A, no significant change in color tone was observed in Samples-B, C, D, and E of the present invention. In order to quantitatively demonstrate this change, the transmission density before and after light irradiation was measured using blue light, green light, and red light. The table shows the decrease in concentration due to light irradiation of the part whose concentration was 1.0 before light irradiation for each sample.

[Table] From the data in the table, it can be seen that compared to sample-A, the decrease in concentration of samples-B, C, D, and E of the present invention is significantly smaller. Example 2 Protection of a reflective coupler print () made by the diffusion transfer method: A 25μ thick polyethylene layer on the back side of the paper, a 20μ thick polyethylene layer containing titanium white on the coated side, and on top of that a 25μ thick polyethylene layer on the coated side. A color photosensitive material was prepared by sequentially coating the following layers on a 15 μm thick oxygen barrier layer consisting of a saponified product of 99.5% ethylene/vinyl acetate copolymer (30:70 mol %). First layer: 2.2 g/m ² of latex particles of poly[styrene-CO-N-benzyl-N,N-dimethyl-N-vinylbenzylammonium chloride-CO-divinylbenzene] and 2.2 g/m ² of gelatin. image-receiving layer, second layer: poly[n-butyl acrylate-CO
The first and second layers are sodium ^salt of 2-hydroxy- ^4,6 -dichloro-S-triazine. hardened by. 3rd layer: stripping layer containing phthaloyl gelatin 1.3g/ ^m2 ; 4th layer: cyan dye-releasing redox compound 0.59g/m2;
cyan dye layer containing g/m ² and gelatin 1.1 g/m ² ; 5th layer: containing 1-[4-(2-formylhydrazino)-phenyl]-3-phenylthiourea as a nucleating agent. Red-sensitive internal latent image type auto-positive
Bromide emulsion silver 1.08gAg/m ² , 5-n-pentadecylhydroquinone-2-sulfonic acid 0.16g/m ²
6th layer: an intermediate layer containing 1.30 g/m ^{2 of} 2,5-di-sec-dodecylhydroquinone and 1.6 g/m ² of gelatin ^; 7th layer: Magenta dye-releasing redox compound
8th layer: 1-[4-( ² -formylhydrazino)-phenyl ^] -3-phenylthiourea as a nucleating agent. Green-sensitive internal latent image type autopositive
Green-sensitive emulsion layer containing silver bromide emulsion 1.35gAg/m ² , 5-n-pentadecylhydroquinone 0.20g/m ² and gelatin 1.4g, 9th layer: 2,5-di-sec-dodecylhydroquinone 1.30g/m 2 ^m2 and gelatin 1.6g/ ^m2 , 10th layer: yellow dye-releasing redox compound
11th layer: Contains 1-[4-( ² -formylhydrazino)phenyl ^] -3-phenylthiourea as a nucleating agent. A blue-sensitive emulsion layer containing a blue-sensitive internal latent image type autopositive silver bromide emulsion of 1.08 g/m ² , 0.16 g/m ² of 5-n-pentadecylhydroquinone-2-sulfonic acid and 1.1 g/m ² of gelatin; 12th layer: layer containing 0.3 g/m ² of 2,5-di-sec-dodecylhydroquinone and 1.3 g/m ² of gelatin. The dye-releasing redox compounds used here were as follows. After sensitometric exposure of this photosensitive material, a 5-micron film of sodium polyacrylate was hardened with 1,4-bis(2',3'-epoxypropoxy)butane on a polyester film base in a dark room. A viscous developer having the following composition was developed between the cover sheets at 32°C to a thickness of 80 microns. Carboxymethyl cellulose sodium salt
60g 5-methyl-1,2,3-benzotriazole
3.5g Sodium sulfite 1.0g 4-methyl-4-hydroxymethyl-1-P-
Tolyl-3-pyrazolidinone 7.5g t-butylhydroquinone 0.3g Benzyl alcohol 1.7g Potassium hydroxide 47g Carbon black 150g Water 730c.c. After 1 minute, peel off the cover sheet together with layers 4 to 12 in hot water at 32℃. A color print with a first and second layer was obtained (reflection print-A). Reflection prints -B to -E were created in the same manner as in Example 1, using the above-mentioned reflection prints instead of the transparency in Example 1. Reflection prints A to E were continuously irradiated for 7 days using a fluorescent lamp fading tester (illuminance 17000 lux) to determine the initial density.
The light resistance was evaluated by measuring the residual rate (%) of the areas where the value was 1.0. The results are shown in the table. From this, it can be seen that Samples -B to -E of the present invention have high light fastness.

[Table] Example 3 Protection of reflective color print () produced by diffusion transfer method: Light-shielding film base 100μ made of polyethylene terephthalate containing carbon black
A color photosensitive sheet was prepared by sequentially applying the following photographic layers thereon. 1st layer: Cyan dye developer 1,4-bis-[β
-(Hydroquinonyl)-α-methylethylamino]-5,8-dihydroxyanthraquinone 0.80
g/m ² , N,N-diethyl laurylamide 0.40g/
layer containing ^m2 and gelatin 0.80g/ ^m2 , 2nd layer: red-sensitive negative silver iodobromide emulsion 2.4gAg/m2;
m ² and gelatin 2.3g/m ² , 3rd layer: intermediate layer consisting of gelatin 2.0g/m ² , 4th layer: magenta dye developer 1-hydroxy-
4-isopropoxy-2-[P(β-hydroquinonethyl)phenylazo]-naphthalene 0.75g/
m ² , N,N-diethyl laurylamide 0.37g/m ²
and gelatin 1.0g/m ² , 5th layer: green-sensitive negative silver iodobromide emulsion 1.0gAg/
^6th layer: intermediate layer consisting of gelatin 1.5g/ ^{m 2} , 7th layer: yellow dye developer 1-phenyl-3
-N-n-hexylcarbamoyl-4-[P-
(β-hydroquinonylethyl)phenylazo-5
- Layer containing 0.5 g/m ^{2 of} pyrazolone, 0.4 g/m ² of N,N-diethyl laurylamide and 0.5 g/m ² of gelatin, 8th layer: Blue-sensitive negative silver iodide emulsion 0.86 g A
9th layer: a layer containing 1.0 g/m ² of auxiliary developer ^{4'-methylphenylhydroquinone and 0.3 g/m 2 of gelatin} . These photographic layers were hardened with the sodium salt of 2-hydroxy-4,6-dichloro-s-triazine. A copolymer of ethylene, vinyl alcohol, and vinyl acetate (mole ratio 70:29.5:
0.5) An oxygen barrier layer of 9.5 g/m ² was provided, and the following layers were further sequentially provided thereon to produce an image receiving sheet. 1st layer: 10 g/m ² layer of half ester of vinyl methyl ether/maleic anhydride copolymer (molar ratio 50:50) with n-butanol, 2nd layer: 5 g/m ² layer of polyvinyl alcohol , and third layer: an image-receiving layer containing 3 g/m ² of poly-4-vinylpyridine and 3 g/m ² of polyvinyl alcohol. These layers were hardened with tri-N-methylolmelamine. After exposing the photosensitive sheet to light having a stepwise exposure for sensitometry, an image-receiving sheet was placed on top of the sheet, and a viscous processing solution having the following composition was spread between the sheets to a thickness of 110 μm. Water 100ml Potassium hydroxide 15g Hydroxyethyl cellulose 4.0g N-benzyl-α-picolinium bromide 2.5g 1,2,3-benzotriazole 1.5g Sodium thiosulfate 0.05g After 1 minute, remove the image-receiving sheet between the photosensitive sheet and the processing liquid layer. A transferred dye image was obtained by peeling it off. (Reflection Print-A) Reflection Prints-B to -E were created in the same manner as in Example 1, using the above-mentioned reflection print in place of the transparency in Example 1. Reflective prints A to E were continuously irradiated for 14 days using a fluorescent light fading tester (illuminance 17,000 lux), and the remaining density (%) of the areas where the initial reflection density was 1.0 was measured, and the light resistance was determined. The gender was evaluated. The results are shown in the table. From now on, samples of the present invention -B to -E
It can be seen that the light fastness is high.

[Table] Example 4 A polyvinyl alcohol (PVA) aqueous solution was coated on one surface of a paper support at 15 g/m ² by rod coating, and after drying, a melt made by adding 15 g of titanium dioxide to 100 g of polyethylene and melting it at about 300°C was applied. of
20g/ ^m2 extrusion coating. Further, the back side was coated with polyethylene alone at 25 g/m ² by melt extrusion. The first layer (lowest layer) listed in the table on the double-sided polyethylene laminated paper thus produced
A color photosensitive material was prepared by sequentially applying the sixth layer (top layer). The coating solution for the first layer was prepared as follows. That is, 100 g of yellow coupler (〓6) was dissolved in 100 ml of dibutyl phthalate and 200 ml of ethyl acetate, and this solution was emulsified and dispersed in 800 g of a 10% gelatin aqueous solution containing 80 ml of a 1% aqueous solution of sodium dodecylbenzenesulfonate. was mixed into 1450 g of blue-sensitive silver chlorobromide emulsion to obtain a coating solution.
Coating solutions for other layers were prepared in the same manner. In the green-sensitive emulsion layer, the following discoloration and fading inhibitor is added to a coupler solvent in which magenta coupler (〓4) is dissolved.
(A) and (B) were added in an amount of 40 mol % based on the coupler. The photosensitive material thus obtained was exposed to light through a color negative, and then subjected to the following development process to obtain a color print (color print -
A). A color print was made in the same manner as in Example 1, except that Color Print-A was used instead of the transparent positive of Example 1, and 2 g/m ² of ultraviolet absorber (C) was added to the adhesive layer of the cover sheet. C, -E
(A, C, and E correspond to Example 1). UV absorber (C)

【table】

[Table] Processing Steps Temperature Time Developing solution 33°C 3 minutes 30 seconds Bleach-fixing solution 33°C 1 minute 30 seconds Water washing 28-35°C 3 minutes The formulation of the processing solution used is as follows. Developer Benzyl alcohol 15ml Diethylene glycol 8ml Ethylenediaminetetraacetic acid disodium salt 5g Sodium sulfite 2g Anhydrous potassium carbonate 30g Hydroxylamine sulfate 3g Potassium bromide 0.6g 4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl) -m-toluidine 2/
Trisulfate monohydrate 5g Adjust the pH to 10.20 and add water to make the total volume 1 Whitening fixer Ethylenediaminetetraacetic acid disodium salt
2g Ethylenediaminetetraacetic acid ferric salt 40g Sodium sulfite 5g Ammonium thiosulfate 70g Add water to total amount 1 This color print - A, C, and E were irradiated with light for 20 days using a fadeometer (100,000 lux) with a xenon arc lamp. Then, we investigated the decrease in density due to light irradiation in the area with an initial density of 1.0 and the stain (change in blue light density) in the white background area. The results are shown in the table.

[Table] From the data in the table, it can be seen that Samples-C and E of the present invention have significantly less decrease in density than Sample-A, have a good balance between the three colors, and have less staining.

Claims (1)

[Claims] 1. In a method for protecting a photographic print image in which the surface of the image layer of the photographic print is protected with a cover sheet, at least one layer of the cover sheet has a saponification degree of 90.
% or more, and the ethylene content is 20 to 69 mol%
and at least one adhesive layer, and the cover sheet and the surface of the image layer are bonded via the adhesive layer. How to protect photographic print images.