JPH0470623B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel color image forming method,
More specifically, the present invention relates to a color image forming method in which processing time is shortened and high quality color images can be easily obtained. With the recent rapid development of electronic technology, it has become possible to record high-quality color images on, for example, optical disks and magnetic tapes. At the same time, there has recently been a strong demand to retrieve the above-mentioned color images as hard copies. Silver halide imaging systems are available on the market. With the non-silver salt image forming systems mentioned above, it is still impossible to reproduce high-quality color images, and on the other hand, existing systems using instant color films also have a problem with the color blue color when inputting high-density images onto the film. It is necessary to use three types of laser light: , green, and red. Regarding writing methods using these three types of laser beams, see NHK Giken Monthly Report, Volume 23, No. 11.
No. 464 (1980), this system is extremely complex and expensive, so it must be said that it is a system that has major problems from the perspective of easily retrieving Nerd copies. Another existing system of CRT photography involves three CRTs that emit monochromatic light.
photograph through a mirror system or emit white light.
There are methods such as placing a three-color separation filter on the CRT surface and multiple exposure three times, but because the CRT's phosphor has granularity, the image quality of the captured image is determined by the image quality on the CRT. However, the disadvantage is that the size of the image is determined by the size of the CRT. The method reported in the above-mentioned NHK Giken Monthly Report and the method of directly photographing CRT are based on Canadian Patent No. 928559, U.S. Patent No. 3415644,
No. 3362819, No. 3415645, No. 3415646, No. 2983606, No. 2543181, No. 3647437,
The laminated integral color diffusion transfer film unit described in British Patent No. 3635707, British Patent No. 1330524, and Canadian Patent No. 674082 is used. In these film units, the photosensitive element is constructed of multiple layers, and the image quality is often significantly degraded due to the long diffusion distance of the diffusible dye. OBJECT OF THE INVENTION An object of the present invention is to improve the above-mentioned prior art and easily create a high-quality color hard disk from a high-quality color image signal recorded on a high-density information recording medium such as a magnetic tape, magnetic disk, or optical disk. An object of the present invention is to provide a method for forming a color image that can be reproduced as a copy. Structure of the Invention As a result of various studies to address the above-mentioned problems, the present inventors have discovered that at least three types of pigment-forming substances capable of releasing pigments or their precursors with different tones are contained in different regions, respectively. A photosensitive element having a mosaic layer in which the regions are arranged in a stripe or mosaic pattern and a photosensitive silver halide emulsion layer sensitive to a wavelength range of 600 nm or more is exposed to monochromatic light through the mosaic layer. Diffusible dyes or diffusible dye precursors that are compatible with imagewise exposure by exposing at least three times to laser light according to the position of each area and contacting with an alkaline processing solution in the presence of a developer. It has now been discovered that this object can be achieved by a color imaging method which generates a unidirectional distribution and diffusely transfers at least a portion of the imagewise distribution to an image-receiving element to form a color image on the image-receiving element. The present invention can shorten the diffusion distance of the dye to the image-receiving layer compared to the conventional case of using a photographic light-sensitive layer with a multilayer structure. Since the monochromatic light that can be used is used, the reproduced image becomes extremely detailed, and a high-quality color image can be obtained. The present invention will be explained in more detail below. The photosensitive element used in the method of the invention is
A layer formed by containing at least three kinds of pigment-forming substances as described above in different regions, and arranging the layers consisting of these regions in a regular stripe shape or a mosaic shape (hereinafter simply referred to as a mosaic layer) The basic structure is to have on a support a photosensitive silver halide emulsion layer and at least one photosensitive silver halide emulsion layer. Further, the image receiving element used in the method of the present invention may contain pigments or pigments that diffuse from the photosensitive element during development by contacting with an alkaline processing solution in the presence of a silver halide developer after exposure of the photosensitive element. It has the function of physically or chemically adsorbing the dye precursor, and may be present integrally with the photosensitive element during exposure, or may be brought into contact with and integrated with the photosensitive element during development. After the color image is formed, the image receiving element and the photosensitive element can be separated, or they can be used while being integrated. Hereinafter, the present invention will be explained in more detail with reference to the drawings. FIG. 1 is a sectional view showing a state in which a mosaic layer 2 according to the present invention is provided on a support (for example, a transparent base) 1. As shown in FIG. Each of the mosaic layers 2 has a minute region, and each region contains a dye-forming substance (Y) that releases a yellow diffusible dye or its precursor, and a magenta diffusible dye or its precursor. A dye-forming substance (M) that releases cyan and a dye-forming substance (C) that releases a cyan diffusible dye or its precursor are selectively contained alternately. FIG. 2 shows a state in which a photosensitive silver halide emulsion layer 3 (sensitized in the infrared wavelength region) is coated on the mosaic layer 2 shown in FIG. FIG. 3 shows the state in which the substrate 2 is exposed to laser light through the support 1 (base surface). Subsequently, after exposure, development with an alkaline processing solution is shown in FIG. 4, but only the area of the mosaic corresponding to the exposed area is developed.
A state in which a diffusible dye (cyan dye in this case) is diffused and transferred from the dye-forming substance contained in the region to the image received by the image receiving element 4 to form a cyan color image is shown. The above has described the case where exposure is given to the image information to develop a cyan color, but similarly, the image information to develop a magenta color and the image information to develop a yellow color are applied by emitting magenta pigment, respectively. By exposing areas of the mosaic layer containing a dye-forming substance capable of obtaining a dye and areas of the mosaic layer containing a dye-forming substance capable of releasing a yellow dye as monochromatic light, magenta and yellow images, respectively, are transferred to an image-receiving element. can be done. FIG. 5 shows another embodiment of the present invention, in which the mosaic layer 2 is a photosensitive silver halide emulsion layer 3.
In this case, the exposure is performed from the opposite side to that shown in FIG. In the present invention, three types of dye-forming substances capable of releasing yellow, magenta, and cyan diffusive dyes or diffusible dye precursors are preferably used as the dye-forming substances as described above. In the present invention, the difference in the maximum absorption wavelength of the dyes produced is
If they are within 50 nm, they are considered to be the same type of pigment-forming substance, even if their structures are different. These different types of pigment-forming substances are contained in different regions arranged in a regular mosaic or stripe pattern. In the present invention, two or more of the above dye-forming substances can be used in combination as long as they are of the same type, even if they have different structures. The above-mentioned striped or mosaic areas may be arranged in any manner, for example, as described in US Pat. No. 3,226,307, US Pat.
The random arrangement described in No. 4007044 etc. may also be used.
Also, Television Society Technical Report Volume 5, Section 556,
The regular arrangement described in Section 609, Volume 6, Section 654, etc. may be used. In the present invention, a gap-free shape with the highest density is preferred, and a rectangular or hexagonal arrangement is particularly preferred, for example. FIG. 6 is a top view showing a specific example of the arrangement of the above regions; FIG. 6A shows an example of a so-called striped layer arrangement, and FIG. 6B shows a mosaic layer arrangement. An array is shown as an example. In the color image forming method of the present invention, the diffusible dye or dye precursor produced in the development process is subtractively mixed and an image is formed while diffusing into the image-receiving layer of the image-receiving element. It is preferable that the containing region is fine, and the finer the area, the better the image quality, particularly the resolution, can be obtained.
Therefore, in the figure, it is preferable that each fine region has a width l of at least 1 μ to 500 μ, particularly 5 μ to 100 μ. Therefore, if desired, these striped or mosaic layers can be made so small that it is impossible to distinguish individual regions even when observed with the naked eye. The mosaic layer used in the present invention can be produced using additive primary multicolor filter arrays well known in the art, such as Finley color color plates or color stripe filters such as those used in Polavision. It can be made using the method used in These methods include, for example, U.S. Patent No. 1003720;
Specifications of No. 2681857 and No. 3284208, Special Publication No. 1972-
17375, 54-13147, JP-A-49-46642, etc., and JP-A-57-104139, JP-A-57-
Examples include a method of forming each filter element in a microcell array provided on a support, as described in Publications No. 104140 and No. 57-115540. The binder for the layer formed in a mosaic or stripe shape according to the present invention is, for example, a hydrophilic binder widely used in photographic materials, specifically gelatin, gelatin derivatives, polyvinyl alcohol, casein, high gelatin binders, etc. Examples include molecular grafted products. The support for the photosensitive element used in the present invention is preferably transparent, and a lenticular lens (Ls) is preferably supported on the back surface on which the photosensitive element is coated, as shown in FIG. The lenticular lens (Ls) is advantageous when dividing the dye-forming substance into different regions in a striped manner, as described in the examples below. Furthermore, when providing image information using a single spectral beam, it is advantageous to expose a desired position by simply changing the exposure angle of the monochromatic light. The dye-forming substance used in the method of the invention is a compound capable of forming an imagewise distribution of a diffusible dye or dye precursor upon development of imagewise exposed silver halide under alkaline conditions. It can be used widely. The imagewise distribution may be a negative image or a positive image with respect to imagewise exposure. The dye-forming substance preferably used in the present invention is oxidized by an oxidized form of a silver halide developer or a compound oxidized by an oxidized form of a silver halide developer to release a diffusible dye or a diffusible dye precursor. or when it is in the reduced form under alkaline conditions, it can release a diffusible dye or diffusible dye precursor, but when it is in the oxidized form, such as when oxidized by an oxidized form of a silver halide developer. is a compound that cannot release a diffusible dye or a diffusible dye precursor under alkaline conditions. Other preferred dye-forming materials include dye developers. The dye precursor referred to herein refers to a substance that undergoes a chemical change during a diffusion process or on the image-receiving layer, or exhibits a hue different from the hue immediately after being released due to a change in physical conditions. Examples of silver halide developers that release dyes when oxidized by oxidants include those described in the following publications. That is,
U.S. Patent No. 4053312, U.S. Patent No. 4055428, U.S. Patent No.
4076529, 4152153, 4135929, JP 53-149328, 51-104343, 53-
46730, 54-130122, 53-3819, Japanese Patent Application No. 54-89128, 54-90806, 54-91187, etc. Among these, those that emit yellow pigment are: U.S. Patent No. 4013633, Japanese Unexamined Patent Publication No. 1983-
No. 149328, No. 51-114930, Patent application No. 148237, No. 149328
Issue, Research Disclosure
Disclosure) 17630 (1978), Disclosure 16475 (1977)
U.S. Patent No. 3954476, U.S. Patent No. 3931144, and U.S. Pat.
No. 3932308, Japanese Patent Publication No. 53-23628, No. 52-106727
No. 54-65034, No. 54-161332, No. 55-
No. 4028, No. 55-36804, Patent Application No. 149777-1977,
There are US Pat.
No. 3929760, No. 4013635, JP-A-51-
No. 109928, No. 53-149328, No. 52-8827, No. 53
−143323, No. 54-47823, Patent application No. 146654
There are numbers etc. In particular, N, N as described in U.S. Pat. No. 4,135,929.
A sulfonamidophenol having a ballast group consisting of a -disubstituted carbamoyl group, a dye-releasing redox compound (DRR compound) having a sulfonamidophenol as a redox center, and a DRR compound represented by the following general formula [] are particularly preferably used. General formula [] In the formula, Col represents a dye or a dye precursor,
Examples of the dye include groups such as azo dyes, azomethine dyes, indoaniline dyes, indophenol dyes, anthraquinone dyes, triphenylmethane dyes, indigo dyes, and metal complex salts thereof. As a dye precursor,
Known leuco dyes and those that give dyes by hydrolysis are listed, and these are disclosed in Japanese Patent Application Laid-Open No. 55-33141.
No. 55-33142, No. 53-35533, No. 55-
It is disclosed in US Pat. No. 53329, US Pat. No. 48-125818, US Pat. No. 3,222,196 and US Pat. In order to avoid the compound from being diffused or washed away in its original form by the alkali used during the processing of the photosensitive element, it requires a ballast group that substantially prevents it from spreading or flowing out. , Ball is an alkyl acylamido group, an arylacyl amide group, an alkyl sulfonamide group,
In the arylsulfonamide group, succinimide group and phthalimide group, R ₁ represents a halogen atom or an alkyl group or alkoxy group having 1 to 3 carbon atoms. The number of carbon atoms in the alkyl group of the alkyl acylamide group and alkyl sulfonamide group shown in Ball
Represents 12 to 20 linear or branched alkyl groups,
Preferably, the aryl group of the arylacylamide group or arylsulfonamide group represents an aryl group substituted with an alkyl group, an alkoxy group, an alkylacylamide group, or an alkylsulfonamide group having 5 to 20 carbon atoms. Further, it is preferable that each of the succiimide group and the phthalimide group is substituted with an alkyl group, alkoxy group, alkylacylamide group, or alkylsulfonamide group having 5 to 20 carbon atoms. R ₂ is tert-butyl group, tert-amyl group, phenyl group and

[Formula] represents a group selected from groups (R ₅ and R ₄ are hydrogen atoms or alkyl groups).
R ₂ is unsubstituted or halogen atom, number of carbon atoms is 1
A phenyl group substituted with a group selected from the group consisting of ~2 alkyl groups or alkoxy groups, acetylamide groups, methylsulfonamide groups, nitro groups, carboxyl groups, sulfo groups, and methylsulfo groups is preferred. m represents an integer from 0 to 3. Examples of the dye-forming substance represented by the above general formula [] suitable for the color image forming method of the present invention are shown below, but the present invention is not limited thereto. Further, examples of redox compounds that release a dye by ring closure in the case of a reduced form include those described in the following publications. That is,
It is described in US Pat. Further, as the above-mentioned dye developers preferably used in the present invention, there are those described in the following publications. That is, U.S. Patent No. 3255001, U.S. Patent No. 3320063
No. 2992106, No. 3297441, No. 3297441, No.
3134762, 3236643, 3134765, 3134764, 3134672, 3134765,
Same No. 3183089, Same No. 3135734, Same No. 3135604,
Same No. 3173906, Same No. 3222169, Same No. 3183090,
Same No. 3201384, Same No. 3246955, Same No. 3208991,
Same No. 3142565, Same No. 2983605, Same No. 3047386,
It is described in the same No. 3076820, the same No. 3173929, the same No. 3230083, etc., and an example thereof is specifically shown below. The coating amount of the dye-forming substance used in the present invention as listed above is 1×10 ⁻⁵ to 1×10 ⁻² mol/m ² ,
Preferably it is 2×10 ⁻⁴ to 2×10 ⁻³ mol/m ² . In addition, there are various methods for adding these pigment-forming substances to the minute regions. For example, they may be added uniformly to each region, or they may be added uniformly to a part of each region, for example, in the form of a stripe. It may be added uniformly. Particularly if the dye-forming substance is colored, a non-uniform addition method is preferred. The pigment-forming substances used in the present invention can be dispersed in the hydrophilic colloid carrier in various ways depending on the type of compound. For example, a compound having a dissociable group such as a sulfo group or a carboxyl group can be dissolved in water or an alkaline aqueous solution and then added to the hydrophilic colloid solution. A solution obtained by dissolving a pigment-forming substance that is difficult to dissolve in an aqueous medium and easily soluble in an organic solvent in an organic solvent is added to a hydrophilic colloid solution and dispersed into fine particles by stirring or the like. Suitable solutions include ethyl acetate, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, β-butoxy-β-ethoxyethyl acetate, dimethylformamide, dimethyl sulfoxide, 2-methoxyethanol, di-n-
Butyl phthalate, etc. Among these dispersing solvents, those with relatively low vapor pressures are either volatilized during drying of the photographic layer, or used in U.S. Pat.
It can also be volatilized by the method described in the same No. 2801171. Among these dispersion solvents, those that are easily soluble in water are disclosed in U.S. Pat.
It can be removed by a water washing method such as that described in No. 3396027. In order to stabilize the dispersion of dye-forming substances and promote the dye image-forming process,
It is advantageous to incorporate the dye-forming substance into the photosensitive element in a solvent that is substantially insoluble in water and has a boiling point of 200° C. or higher at normal pressure. Suitable high-boiling solvents for this purpose include triglycerides of higher fatty acids, aliphatic esters such as di-octyl adipate, di-
Phthalate esters such as n-butyl phthalate, tri-o-cresyl phosphate, tri-
Examples include phosphoric acid esters such as n-hexyl phosphate, amides such as N,N-diethyl laurylamide, and hydroxy compounds such as 2,4-di-n-amylphenol. Additionally, it is advantageous to incorporate a hydrophilic polymer with the dye-forming material in the photographic element to stabilize the dispersion of the dye-forming material and facilitate the dye image forming process. Philic polymers suitable for this purpose include: sierac; phenol formaldehyde condensates; poly-n-butyl acrylate; copolymers of n-butyl acrylate and acrylic acid; n-butyl acrylate, copolymers of styrene and methacrylamide; etc. These polymers may be dissolved in an organic solvent together with a dye-forming substance and then dispersed in a hydrophilic colloid, or a hydrosol of the polymer prepared by emulsion polymerization or the like may be added to a hydrophilic colloid dispersion of a dye-forming substance. May be added. Dispersion of dye-forming substances is generally effectively achieved under high shear forces. For example, high-speed rotating mixer, colloid mill,
High pressure milk homogenizer, British Patent No. 1304264
The high-pressure homogenizer, ultrasonic emulsifier, etc. disclosed in this issue are useful. Dispersion of dye-forming substances is greatly aided by the use of surfactants as emulsion aids. Surfactants useful in dispersing the color-forming substances used in the present invention include sodium triisopropylnaphthalene sulfonate;
Sodium dinonynalphthalene sulfonate, p
-There are anionic surfactants such as sodium dodecylbenzenesulfonate, dioctylsulfosuccinate sodium salt, sodium cetyl sulfate salt, and anionic surfactants disclosed in Japanese Patent Publication No. 39-4293, and these anionic surfactants and anhydrohexitol The combination with higher fatty acid esters shows particularly good emulsifying ability as disclosed in US Pat. No. 3,676,141. The photosensitive silver halide emulsion layer used in the present invention may be composed of two or more layers having different sensitivities. The silver halide used in the layer is, for example, silver halide having a mixed composition such as silver chloride, silver bromide, silver iodide or silver chlorobromide. Further, as the binder for the silver halide emulsion layer, the same hydrophilic binder as used in the above-mentioned mosaic layer can be used. The silver halide emulsion layer containing these silver halides contains activated gelatin, a sulfur sensitizer such as allylthiocarbamide, thiourea, cystine, etc.
Chemical sensitization can be carried out using a selenium sensitizer, a noble metal sensitizer, for example, a gold sensitizer, or a sensitizer such as ruthenium, rhodium, or iridium, either alone or in combination as appropriate. In the method of the present invention, it is preferable to use a semiconductor laser as the light source of monochromatic laser light for exposure. Various sensitizing dyes are used to impart photosensitivity in the wavelength range of 600 nm or more, but
Representative pigments include cyanine, merocyanine, trinuclear or tetranuclear cyanine, styryl, hemicyanine, oxonol, and hemioxonol. As cyanine dyes, those having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole, and imidazole are preferable, and such a nucleus includes an alkyl group, an alkylene group, a hydroxyalkyl group, and a sulfoalkyl group. , a carboxyalkyl group, an aminoalkyl group, or an enamine group capable of forming a fused carbocyclic or heterocyclic ring. Furthermore, it may be symmetrical or asymmetrical, and may have an alkyl group, phenyl group, enamine group, or heterocyclic substituent on the methine chain or polymethine chain. In addition to the above-mentioned basic nucleus, the merocyanine dye may have an acidic nucleus such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a valpituric acid nucleus, a thiazolinthione nucleus, a malononitrile nucleus, or a pyrazolone nucleus. good. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamino group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindenes, cadmium salts, organic sulfonic acids, etc., such as U.S. Pat. No. 2,933,390
A supersensitizing additive that does not absorb visible light, such as those described in No. 2937089 and the like, can be used in combination. In addition, 12-
Acetoxy-3,3'-diethylthiatetracarbocyanine perchlorate, 12-acetoxy-3,
3'-diethylthiapentacarbocyanine perchlorate, 3,3'-diethyl-9,11-neopentylenethiatetracarbocyanine iodide,
3,3'-diethyl-9,11,15,17-dineopentylene-thiapentacarbocyanine iodide, neocyanine, 3,3'-diethyl-5,5'-
Diphenylthiatricarbocyanine ethyl sulfate, 3,3'-diethyl 5,5',6,6'-tetramethoxythiatricarbocyanine iodide, 3,3'-diethylthiatricarbocyanine bromide, 3-ethyl -3'-sulfopropyl-
5,5' dichlorothiadicarbocyanine, 3,3'-
Sulfopropyl-6,6′-dimethyl-thiadicarbocyanine, 2-{5′-(3″-ethyl-naphtho[2,1-α]thiazolidene)penta-1′,3′-
diethyl}-3-ethylnaphtho[2,1-α]thiazolyl bromide, 3,3'-diethylthiatricarbocyanine bromide, 3,3'-diethyl-
Selenatricarbocyanine bromide, 3,3'-
Allyl-5,5',6,6'-methoxythiatricarbocyanine, 3,3'-methyl-oxatricarbocyanine, 1,1'-sulfopropyl-4,4'-dicarbocyanine, 2-[ 3′-Methyl-5-{3″-ethyl-naphtho[2,1-α]thiazoliden}penta-1′,3′dienyl]-3-ethyl-naphtho[2,
1-α]thiazolium iodide, and others,
Cyanine having a structure in which a cyclic group is introduced into a part of the methylene chain in order to stabilize and fix a long methylene chain, such as 2-{3,3-dimethyl-5
(3-ethyl-benzthiazolidenmethylidene)-
5-Cyclohexenylidenepropenyl}-3-ethylbenzthiazolinium iodide, 2-
{3,3-dimethyl-5-(3-ethylbenzthiazolidenmethylidene)-5-cyclohexenylidenebentadienyl}-3-ethylbenzthiazolinium iodide, also 2-{5-(3- Ethylbenzthiazolinideneethylidene)-4-oxothiazolin-2-yl-pyropylidene}-3-ethylbenzthiazole, 3-(3-ethylbenzthiazolinylidene-butadienylidene)-6-(3-
Ethyl-benzthiazolinylidenehexatrienylidene)-hexane-1,2,4,5-tetra-
Examples include on. Also many other cyanines,
Many other polynuclear dyes are available, such as merocyanine. This silver halide emulsion also contains triazoles,
It can be stabilized with tetrazoles, imidazoles, azaindenes, quaternary benzothiazolium compounds, zinc or cadmium compounds,
It may also contain a quaternary ammonium salt type or polyethylene glycol type sensitizing compound.
It may also contain suitable gelatin plasticizers such as glycerin, dihydroxyalkanes such as 1,3-pentanediol, esters of ethylene bisglycolic acid, bis-ethoxydiethylene glycol succinate, amides of acrylic acids, latex, etc. can also be used for formaldehyde, halogen-substituted fatty acids such as mucobromic acid, compounds with acid anhydride groups, dicarboxylic acid chlorides,
gelatin hardeners such as biesters of methanesulfonic acid, sodium bisulfite derivatives of dialdehydes in which the aldehyde groups are separated by divalent or trivalent carbon atoms, or spreading agents such as saponins;
Alternatively, various photographic additives such as coating aids such as sulfosuccinates can be contained. Furthermore, various additives commonly used in photography, such as antifoggants and ultraviolet absorbers, can also be included, if necessary. In the present invention, as described above, various silver halide emulsions can be used, and when a negative silver halide emulsion is used, a negative color diffusion transfer image can be obtained. Positive color diffusion transfer images can be obtained by various methods. The image-receiving layer of the image-receiving element used in the present invention may also contain other additives such as a photofading inhibitor, a fluorescent brightener, and an ultraviolet absorber. Various known photofading inhibitors can be used, including 2,6-t-butyl-p-
Specific examples include cresol, 2,2'-methylenebis(4-methyl-6-t-butyl-phenol), and 4,4'-thiobis(3-methyl-6-t-butyl-phenol). . As an ultraviolet absorber, 2-(3',5'-ditor
Cyariamyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-ditacylphenyl)5-chlorobenzotriazole, 2-(3',5'-ditacylphenyl) Butyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)
Benzotriazole, 2-(hydroxy-5-tertiarybutylphenyl)benzotriazole,
2-hydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-n
-Octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-ethylhexyl-2-
Cyano-3,3'-diphenyl acrylate, p-
Various known compounds can be used, such as octylphenyl salicylate and 2,4-ditertyabutyl phenyl-3,5-ditertyabutyl-4-hydroxybenzoate. As the fluorescent whitening agent, various known compounds such as stilbenes, coumarins, carbostyrils, diphenylpyrazolines, naphthalimides, and arylazolyls are used. Specific examples include whitefluor B, whitephore PCN (Sumitomo Chemical), Hakkol PY-1800, Hakkol PY-2000, and Hakkol PY-2000.
PY-B (both Showa Kagaku), Kayalight B, same
08 (Nippon Kayaku), High Bright 1001 (Dainichiseika),
Uvitex CB (ciba-Geigy), Mikephore ETM
There are commercially available products such as (Mitsui Toatsu). The image-receiving element according to the invention may be integrated with the photosensitive element or may be placed on a separate support adapted to be superimposed on the photosensitive element after exposure. The image-receiving layer of the image-receiving element used in the present invention can be any material, so long as the material mordantes or otherwise fixes the dyes that diffuse into the layer. The particular material selected here will, of course, depend on the dye to be mordanted, but generally polymeric mordants can be used. These polymer mordants are polymers containing secondary and tertiary amino groups, polymers having nitrogen-containing heterocyclic moieties, polymers containing these quaternary cation groups, etc., and have a molecular weight of 5,000 to 200,000, especially 10,000 to 50,000.
belongs to. For example, US Patent No. 2548564, US Patent No. 2484430,
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in Specification No. 3148061, Specification No. 3756814, etc.; Polymers containing dialkylamino groups disclosed in Specification No. 2675316; Aminoguanidine derivatives disclosed; No. 3625694, No. 3859096,
Polymer mordants capable of crosslinking with gelatin etc. disclosed in U.S. Patent No. 4128538, British Patent No. 1277453, etc.; U.S. Patent No. 3958995, U.S. Pat.
Aqueous sol-type mordant disclosed in Specification No. 2798063, etc.; Water-insoluble mordant disclosed in Specification No. 3898088;
No. 3788855, No. 3642482, No. 3488706, No. 3557066, No. 3271147, No. 3271148,
JP-A-50-71332, JP-A No. 53-30328, JP-A No. 52-
No. 155528, No. 53-125, No. 53-1024, No. 54-
No. 74430, No. 54-124726, No. 55-22766, No. 55
Mention may be made of the mordants disclosed in Patent No. 142339 and publications. When a PH value lowering layer containing a PH value lowering substance is used in the image receiving element according to the present invention, the stability of the transferred image can be increased. Typically, the PH-lowering material reduces the PH of its image-receiving layer from about 13 or 14 to at least 11 within a short period of time after swelling.
, preferably 5 to 8. For example, polymeric acids as disclosed in U.S. Pat. No. 3,862,819 or U.S. Pat.
Good results can be obtained using solid acids or metal salts, such as zinc acetate, zinc sulfate, magnesium acetate, etc., as disclosed in US Pat. No. 2,584,030. Such PH value lowering substances lower the PH value of the image receiving layer after development to terminate development and essentially reduce subsequent dye transfer, thus stabilizing the dye image. In embodiments of the invention, an inert timing or spacer layer may be used adjacent to the PH-lowering layer. Such an inert layer "temporally adjusts" or controls the decrease in the PH value as a function and effect of the rate when alkali diffuses into the interior of the above-mentioned inert spacing layer. In the present invention, when the image receiving element is integrated with a photosensitive element, a cover sheet is disposed on the opposite side of the photosensitive layer of the photosensitive element from the image receiving element, and the cover sheet and the photosensitive layer are connected to each other. The alkaline treatment composition is adapted to be released between the two.
Preferred cover sheets contain a support and a PH value lowering layer supported thereon and at least one timing layer (also referred to as a spacer layer or "inert spacer layer"). Suitable materials for use in the neutralization layer and timing layer include Research Disclosure,
Vol123, Section 12331, July 1974 and Vol135,
Section 13525, July 1975. In the method of the present invention, image information is written from a high-density information recording medium or the like using monochromatic light. As the monochromatic light, a wide variety of known laser lights can be used, and all laser lights having an oscillation wavelength in the red or infrared light region are preferably used. Regarding semiconductor lasers that are particularly preferably used in the present invention, specific examples of semiconductor lasers include Ga ₁ -x AlxAs/GaAs (700 to 900 n
m), _In1 −xGaxAsl−yPy/InP (900 to 1700 nm),
In ₁ −xGaxAsl−ySby/GaSb (1700~4000nm)
Semiconductor lasers using materials such as
The semiconductor laser that can be used as a light source for exposing the photosensitive material of the present invention is a semiconductor laser having an oscillation wavelength in the range of 600 to 1000 nm.
It is a semiconductor laser with an oscillation wavelength of ~1000 nm. In the present invention, the silver halide developer used to develop the photosensitive element can be contained in an alkaline processing solution or in any layer of the photosensitive element or image-receiving element. It is also possible to act on the silver halide emulsion only by supplying the alkaline processing liquid.
Examples of silver halide developers that can be used in the present invention are as follows. Hydroquinones, aminophenols (e.g. N-methylaminophenol), 3-pyrazolidinones (e.g. 1-phenyl-3-pyrazolidinone, 1-phenyl-4,4-dimethyl-3
-pyrazolidinone, 4-hydroxymethyl-4-
Methyl-1-phenyl-3-pyrazolidinone, 4
-Hydroxymethyl-4-methyl-1-tolyl-
3-pyrazolidinone), phenylenediamines (e.g., N,N-diethyl-p-phenylenediamine, 3-methyl-N,N-diethyl-p-phenylenediamine, 3-methoxy-N-ethoxy-p- phenylenediamine), reductones, etc.
Among those listed here, black and white developers are particularly preferred, as they generally have properties that reduce stain formation in the image receiving layer (mordant layer). Preferably, the silver halide developer for inclusion in the light-sensitive or image-receiving element is a precursor such as that described in JP-A-55-53330, particularly as described in British Patent No.
It is desirable that the silver halide developer is stabilized with a metal salt or the like as described in No. 2056101. The processing composition used in the present invention is a liquid composition containing the processing components necessary for developing a silver halide emulsion and forming a diffusion transfer dye image, and the solvent is mainly water and methanol is also used. may also contain hydrophilic solvents such as methyl cellosolve. The processing composition maintains the pH necessary for development of the emulsion layer and removes acids generated during the development and color image formation processes (e.g., hydrohalic acids such as hydrobromic acid, carboxylic acids such as acetic acid). Contains a sufficient amount of alkali to neutralize acids (acids, etc.). Examples of alkalis include alkali metal or alkaline earth metal salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbonate, trisodium phosphate, diethylamine, or amines. is used, preferably having a pH of about 12 or higher at room temperature, especially
It is desirable to contain caustic alkali at a concentration such that the pH is 14 or higher. When a silver halide developer is initially incorporated exclusively into a photographic element consisting of a light-sensitive element and an image-receiving element, the remaining components normally present in the developer (e.g., water, activators and preservatives) may constitute what is commonly referred to as an activator solution. The activator solution is identical in composition to the silver halide developer solution, except for the absence of silver halide developer, and is used when the silver halide developer is incorporated into the photographic element. . In the present invention, references hereinafter to developer compositions are intended to include both silver halide developer solutions and activator solutions. The processing composition may also contain light-absorbing substances such as carbon black and PH indicator dyes, as described in U.S. Pat. No. 3,579,333, to prevent fogging of the silver halide emulsion by external light during processing. It may be advantageous in some cases to contain desensitizers such as those described above. Furthermore, a development inhibitor such as benzotriazole can be added to the processing liquid composition. In addition, the present alkaline processing composition may contain substances that promote development or dye diffusion, such as benzyl alcohol, glycols and/or amino alcohols described in JP-A-52-127233,
Compounds such as saturated aliphatic alcohols or saturated alicyclic alcohols described in JP-A-55-74541 may also be included. In particular, it is preferable to contain fatty acids and aliphatic primary amines such as 11-aminoundecanoic acid and/or 6-aminohexanoic acid described in JP-A-53-81119. In addition, in order to improve the immersion properties of the processing agent components,
For example, a buffer agent described in Research Disclosure, 19565, 19566 may be added. In a preferred embodiment of the invention, processing solution is absorbed into the exposed photosensitive element from a non-viscous processing solution, such as by passing the exposed photosensitive element into a container of processing solution. It is also possible to use conventional techniques that allow the required small amount of processing solution to be applied virtually uniformly over the surface of the negative, such as by passing the processing solution through, as disclosed in U.S. Pat. No. 3,194,138. A liquid application device with a capillary gap may also be used. The required amount of processing solution is applied from the viscous processing composition to the sensitizer, provided that there is no layer of polymer or processing composition between the light-sensitive element and the image-receiving element when they are later superimposed. It is also possible to absorb it into the elements.
However, it is preferred to use non-viscous processing solutions, as this allows the use of very simple processing equipment and handling techniques. Despite the special technology for supplying the processing solution to the photosensitive element, the receiving element is placed between the wetted photosensitive element and the front surface.
It is kept dry until front contact, so that the image receiving element is necessarily wetted only by the processing solution extracted from the photosensitive element. The expression "front-to-front contact" is used in the present invention to indicate that there is no layer of processing composition between the superimposed photosensitive element and image receiving element. The expressions "non-viscous processing solution" and "non-viscous processing composition" as used in the present invention are intended to refer to a processing solution or composition having a viscosity substantially similar to water. . Preferably 100 cp or less at 24°C, more preferably 10 cp
It has the following viscosity. Non-viscous processing compositions do not contain polymeric film-forming substances or other viscosity-imparting components such as those used in commercially practiced color diffusion transfer processes. Generally, non-viscous processing solutions suitable for use in the present invention are obtained from processing compositions of the type described in the prior literature by simply removing the film forming agent. In some cases, such non-viscous compositions transfer a partially solidified layer of the processing composition to either of the exposed light-sensitive elements and image-receiving elements when the elements are separated from their superimposed relation. It may also contain a reagent whose primary function is to facilitate adhesion to the material, and since this function is not utilized in the method of the present invention, such a reagent may be omitted. In some cases, the new processing techniques of the present invention reduce the concentration of one or more agents in a treatment composition compared to the concentration when the agent is used in a viscous treatment composition. became possible. The particular concentration of a given agent to be used in a non-viscous treatment composition can be readily determined by one skilled in the art by performing routine concentration tests. As previously pointed out, the non-viscous processing composition can be applied to the photosensitive element in a number of ways, such as by applying the non-viscous processing composition to the exposed photosensitive element by the block or head of a porous application device. or by passing the exposed photosensitive element through a container of the non-viscous processing composition. The method of contacting the photosensitive element according to the present invention with the non-viscous processing composition includes a method of immersing the photosensitive element in an alkaline processing bath, a method of spraying the photosensitive element,
An example of a method of supplying the material is by brushing or painting. For example, US Patent No. 3103153, US Patent No. 3112685, US Patent No.
No. 3195435, No. 3626832, No. 3695163,
Relating to an apparatus for an image transfer processor in which a photosensitive element is passed through a tank or container holding a processing composition, and then the photosensitive element is pulled out of the container and superimposed on an image receiving element, simultaneously or subsequently pressed into front-to-front contact. Although these apparatuses have been described and may be utilized in practicing the present invention, it is particularly preferred to process using an image transfer processor of the type described in US Pat. No. 4,223,991. Referring to the drawings, FIG. 8 shows that the exposed photosensitive element 5 is immersed in a container 7 of a non-viscous processing solution 6 for a period of time and then removed from the container and passed between pressure rollers 9 and 10 with a dry receiver element 8. This indicates that there will be front-to-front contact with this. Since the pressure rollers 9 and 10 only press the polymer 11 consisting of the photosensitive element 5 and the image receiving element 8, a viscous processing liquid must be distributed between the two sheets, a so-called self-processing camera. Pressure rollers 9 and 10 may be of simple construction and equipment compared to the rollers used in the invention. A squeeze roll or other device may be provided to remove excess processing solution adhering to the front and/or back surface of the photosensitive element as it is withdrawn from the processing solution 6 prior to superimposing the photosensitive element onto the dry receiver element. . In order to ensure that the tips and side edges of the photosensitive element and the image receiving element pass between the pressure rollers 9 and 10 without misalignment, the tips of the photosensitive element and the image receiving element are shifted in advance before passing between the rollers. It is desirable to align the tips of the photosensitive element and the image receiving element when they are inserted into the holding roller, and a processor having such a device is described in the above-mentioned U.S. Pat.
Described in No. 422991. Although a support for the photosensitive element according to the present invention is not necessarily required, a support that does not undergo significant dimensional changes during development processing is suitable. As the support, plastic films such as cellulose acetate film, polystyrene film, polyester film, and polycarbonate film, which are used in ordinary photographic materials, are mainly used, but paper supports can also be used. Furthermore, in order to enable development processing in a bright room, light-shielding agents such as carbon black are used at appropriate locations on photographic elements with various layer configurations.
It is desirable to shield from light. In this case, an optical density of about 5 to 10 is required. Appropriate light-shielding positions vary depending on the layer structure of the photographic element, but a light-shielding agent such as carbon black or titanium oxide is placed in the support and/or on the opposite side of the silver halide emulsion layer to an optical density of 5 to 10. It can be added as desired. It is also preferred to provide a white layer in the photographic element as a background for the image if it does not peel off after image formation. Although a support for the image-receiving element is not necessarily required, the supports that may be used include polymeric films, wood fibers such as paper, metal sheets and foils, glass, ceramics, and the like. The support has one or more undercoat layers in order to improve the adhesion, antistatic properties, dimensional stability, peeling resistance, hardness, friction properties, and/or other properties of the support surface. . Common useful polymeric film supports include films of cellulose nitrate esters, such as cellulose triacetates and diacetates, polystyrene, polyamides, homo- and copolymers of vinyl chloride, poly(vinyl acetals), polycarbonates, olefins. Homo- and copolymers of
Examples are polyethylene and polypropylene, and polyesters of dibasic aromatic carboxylic acids and dihydric alcohols, such as poly(ethylene terephthalate). Common useful paper supports are partially acetylated or partially acetylated polymers of parita and/or polyolefins, especially α-olefins having from 2 to 10 carbon atoms, e.g. It is coated with polyethylene, polypropylene, a copolymer of ethylene and propylene, etc. Particularly useful supports for use in image-receiving elements preferably provide a good background for the transferred image and preferably have a reflectance of about 80% or higher. Particularly preferred are polymer films containing white pigments such as Tio ₂ , kaolin, mica, barium sulfate, and zinc oxide. Furthermore, the support may be subjected to an opaque treatment as described in Research Disclosure No. 18336, so that the silver halide photosensitive layer is not fogged by light. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 70 ml of methanol, 1.25 g of nitrocellulose and 30 ml of n-butanol were placed on the front side (flat side) of a polyethylene terephthalate film base having a cellulose acetate butyrate layer containing 16 lenticular lenses per millimeter on the back side. A subbing layer consisting of was applied. Next, on the above subbing layer, a 10% gelatin aqueous solution in which the exemplary compound of the present invention ((18), 5.9 g, di-n-butyl phthalate, 5 g) was dissolved and protected and dispersed.
The first gelatin was prepared by applying a composition consisting of 200 ml and 3 g of potassium dichromate, exposing it to ultraviolet light to harden a portion, and then washing with warm water at 50° C. to remove the unhardened portion. Got layers. Further, on top of this first gelatin layer, a second gelatin layer was formed in the same manner as above except that 5.0 g of exemplified compound (4) was used instead of exemplified compound (18) and the irradiation angle of ultraviolet rays was changed. A gelatin layer was created. Furthermore, a third gelatin layer was placed on the second gelatin layer in the same manner as above except that 5.2 g of the exemplified compound (3) was used instead of the exemplified compound (18) and the irradiation angle of the ultraviolet rays was changed. A gelatin layer was created. On the striped filter layer thus obtained, a silver halide emulsion having the composition shown below was coated as a photosensitive layer in an amount of 5.0 mg of silver per 100 cm ² to obtain a photosensitive element. (Composition of photosensitive layer coating solution) Monodisperse octahedral emulsion with a grain size of 0.4 μm containing 0.353 mol of silver and 50 g of gelatin per 1 kg of silver bromide emulsion...100 ml sensitizing dye 3-(3-ethyl-benzothiazolinidene) 0.05 wt% methanol solution of tadienylidene)-6-(3-ethyl-benzothiazolinylidene-hexatrienylidene)-hexane-1,2,4,5-tetraone...15ml Photosensitive element prepared as above A semiconductor laser printer (5mW.GaAlAs laser, oscillation wavelength 780nm) has a configuration block as shown in Figure 9.
I did the exposure. FIG. 10 shows a laser beam scanning optical system used in the above exposure. In the figure, 21 is a photosensitive element, 22 is an fθ lens, 23 is a rotating polygon mirror, 24 is a correction optical system, 25 is a beam converter, 26 is a collimation optical system, 27 is a semiconductor laser, and 28 is a photosensor. Exposure is performed by changing the angle of incidence on the drum-shaped photosensitive element so that laser beams modulated by blue, green, and red electrical signals are irradiated onto the photosensitive areas corresponding to the yellow, magenta, and cyan line stripes, respectively. , I went there three times. The output control and modulation method of the semiconductor laser at this time is shown in FIGS. 11, 12, and 13. After exposure, the photosensitive element is immersed in a developer having the composition shown below for 20 seconds, superimposed on an image receiving element prepared by applying the following coating liquid to resin-coated paper, and placed between the pressure rollers of the processor shown in Figure 8. Through, 2
After standing for a minute, the photosensitive element and image receiving element were separated, and the image receiving element was washed with a 0.5% acetic acid aqueous solution. (Developer composition) Potassium hydroxide 37g Benzyl alcohol 8ml 11-aminoundedecanoic acid 2g 5-methylbenzotriazole 4.6g Potassium bromide 2g Methylhydroquinone 3.2g Add water to make 1. (Image-receiving element coating composition) Poly(styrene-co-N,N-dimethyl-N-
Benzyl-N-P-(methacryloylaminophenyl)methylammonium chloride-cordivinylbenzene) 5.4g Gelatin 5.4g Tetrakis(vinylsulfonylmethyl)methane
Add 0.07g water to make 200ml. A good yellow wedge image was obtained on the receiving element by diffusion transfer from a photosensitive element exposed by a laser beam modulated by a blue electric signal, and a good yellow wedge image was obtained by diffusion transfer from a photosensitive element exposed by a laser beam modulated by a green electric signal. A good magenta wedge image was obtained on the image-receiving element, and a good cyan wedge image was obtained on the image-receiving element that was diffuse-transferred from a photosensitive element exposed to a laser beam modulated by a red electric signal. A good black wedge image was obtained on the image receiving element which was diffusely transferred from the photosensitive element which was wedge exposed three times with a laser beam modulated by blue, green and red electrical signals. Table 1 below shows the minimum and maximum densities of color images obtained on each of the above image receiving elements.

Table 2 below also shows the density of the black image obtained by three laser beam exposures as described above, with respect to blue light, green light, and red light.

[Table] As is clear from Table 1 above, according to the present invention, by developing the photosensitive element exposed to laser light corresponding to each color light, an excellent diffusion transfer color can be transferred onto the superimposed image receiving element. It can be seen that an image is obtained. Furthermore, from the results in Table 2, it is clear that the density of the black image on the image-receiving element obtained by the method of the present invention with respect to each color light is almost uniform. This can be understood as proving that each fine region has the ability to uniformly receive the laser light and uniformly emit each pigment of different tone. Effects of the Invention According to the present invention, a high-quality color image signal recorded on a high-density information recording medium can be quickly and easily recorded and reproduced as a high-quality hard copy.

[Brief explanation of the drawing]

1 and 2 are cross-sectional views showing the structure of the photosensitive element according to the present invention, FIG. 3 is a state diagram showing the photosensitive element exposed to laser light, and FIG. 4 is a state diagram showing the image receiving layer formed by the exposure. FIG. 5 is a phase diagram showing the diffusion of the dye released into the atmosphere, and FIG. 6A is a sectional view showing the structure of a photosensitive element as another embodiment of the present invention.
FIGS. 3A and 3B are top views showing the arrangement of minute regions of a mosaic filter layer of a photosensitive element according to the present invention. FIGS. FIG. 7 is a cross-sectional view showing the structure of a photosensitive element according to still another embodiment of the present invention, and FIG. 8 is a cross-sectional view showing the structure of a processor for developing the photographic element of the present invention. Furthermore, FIG. 9 is a block diagram of a laser printer used to expose a photosensitive element according to the present invention, and FIG.
Fig. 0 is a schematic diagram showing the laser beam scanning optical system in the above printer, Fig. 11 is a schematic diagram showing the output control signal of the above printer, and Fig. 12 is a schematic diagram showing the output control signal of the above printer.
13 in the semiconductor laser output control block diagram in the semiconductor laser exposure apparatus used in the present invention.
The figure is an overview diagram showing pulse modulation of a semiconductor laser in the same device. DESCRIPTION OF SYMBOLS 1...Support, 2...Mosaic layer, 3...Photosensitive silver halide emulsion layer, 4...Image receiving layer, 5...Photosensitive element.

Claims (1)

[Claims] 1. A mosaic layer in which at least three types of pigment-forming substances capable of releasing pigments or pigment precursors with different tones are contained in different regions, and the regions are arranged in regular stripes or mosaics, and A photosensitive element having a photosensitive silver halide emulsion layer sensitive to a wavelength range is exposed through the mosaic layer to each area with monochromatic laser light at least three times in accordance with the position of each area. A distribution of a diffusible dye or a diffusible dye precursor corresponding to imagewise exposure is produced by contacting an alkaline processing liquid in the presence of a developer, and at least a portion of the imagewise distribution is transferred to an image-receiving element. A method for forming a color image, which comprises performing diffusion transfer to form a color image on an image-receiving element.