JPH0475493B2 - - 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 been a growing demand for the ability to retrieve the color images mentioned above as hard copies.
In response to this demand, non-silver salt image forming systems such as thermal transfer systems and inkjet systems, and silver salt image forming systems using instant color films and the like have been provided 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 Technical Monthly, Volume 23, Vol.
No. 11, p. 464 (1980),
This system is very complex and expensive;
It must be said that this system has a major problem from the viewpoint of easily retrieving hard copies.
Another existing system for taking pictures of CRTs involves three monochromatic lights.
There are methods such as photographing a CRT through a mirror system, or placing a three-color separation filter on the CRT surface that emits white light and performing multiple exposure three times, but due to the granularity of the CRT's phosphor, the image quality of the photographed image is but
It has the disadvantage that the image quality is determined by the image quality on the CRT, and the size of the image is determined by the size of the CRT. The method reported in the above-mentioned NHK Technology 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. Purpose of the invention The purpose of the present invention is to improve the above-mentioned prior art,
An object of the present invention is to provide a color image forming method that easily reproduces a high-quality color hard copy from a high-quality color image signal recorded on a high-density information recording medium such as a magnetic tape, a magnetic disk, or an optical disk. Structure of the Invention As a result of various studies for the above-mentioned purpose, 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 having sensitivity to light in a photosensitive wavelength range of 600 nm or more is passed through the mosaic layer to each of the above dyes. At least three types of regions where the forming substances are present are matched to color images corresponding to the respective pigment forming substances,
Exposure to monochromatic light in at least three portions and contacting an oxidized form of the developer in the presence of a developer produces a distribution of the diffusible dye or diffusible dye precursor corresponding to imagewise exposure. It has been found that the above objects can be achieved by a color imaging method in which at least a portion of the imagewise distribution is diffusely transferred to an image-receiving element to form a color image on the image-receiving element. The present invention can shorten the diffusion distance of dyes compared to conventional multilayer photosensitive elements,
Furthermore, since monochromatic light whose spot diameter can be narrowed down is used to write information, the reproduced image becomes extremely dense 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 (hereinafter simply referred to as a mosaic layer) formed by containing at least three types of pigment-forming substances as described above in different regions, and arranging the layers consisting of these regions in a striped or mosaic shape; The basic structure is to have at least one photosensitive silver halide emulsion layer on a support. 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 minute regions, each of which contains a dye-forming substance Y that releases a yellow diffusible dye or a precursor thereof, and a dye-forming substance Y that releases a magenta diffusible dye or a precursor thereof. A dye-forming substance M that releases a cyan diffusible dye or a dye-forming substance C that releases a cyan diffusible dye or a precursor thereof 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. The state in which layer 2 has been exposed to laser light through support 1 (base surface) is shown in FIG. 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, and the dye-forming substance contained in the area is removed. A state in which a diffusible dye (in this case, cyan dye) is diffusely transferred to the image receiving surface of the image receiving element 4 to form a cyan color image is shown. The above describes the case in which exposure is given to image information to produce a cyan color, but similarly, image information to produce a magenta color and image information to produce a yellow color are each given a magenta dye. 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, exposure is performed from the opposite side to that shown in FIG. In the present invention, three types of pigment-forming substances capable of releasing yellow, magenta, and cyan diffusive pigments or their precursors are preferably used as the pigment-forming substances as described above, and the maximum absorption wavelength of the produced pigment is If the difference is 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 mutually different regions arranged in a mosaic or striped 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, Technical Report of the Television Society, 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 is an additive primary color multicolor filter array well known in this technical field, such as an autochrome plate used in Lumiere color, an Agfa color plate, a Finley color color plate, etc. Alternatively, it can be manufactured using a method used to manufacture color stripe filters such as those used in Polavision. These methods include, for example, US Patent No. 1003720, US Patent No. 2681857,
Specifications of No. 3284208, Special Publication No. 52-17375, No. 52
-17375, 54-13147, JP-A-49-46642, etc., as well as JP-A-56-500272,
JP-A No. 57-104139, No. 57-104140, No. 57-
Examples include a method of forming each filter element in a microcell array provided on a support, as described in various publications such as No. 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 distributing the dye-forming substance into different areas in a striped manner, as described in Examples below. Furthermore, when providing image information with monochromatic light, 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 present invention is widely used as long as it is a compound capable of forming an image-wise distribution of a diffusible dye or dye precursor when developing silver halide imagewise exposed to light. can do. The imagewise distribution may be a negative image or a positive image with respect to imagewise exposure. In the present invention, the dye precursor released from a dye-forming substance refers to a compound that undergoes a chemical or physical change during a diffusion process or on an image-receiving element, thereby emitting a hue different from the hue immediately after release. . The dye-forming substance used in the method of the present invention is a compound capable of coupling with an oxidized silver halide developer to release a diffusible dye or dye precursor, and is represented by the following general formula (). I can do it. General formula () A-B-C In the formula, A is a coupler residue, B is a bond and is a monovalent or divalent linking group, and C represents a dye or dye precursor residue. Moreover, it is preferable that B binds to the active site of A. In the above general formula (), examples of the coupler residue represented by A include diketomethylene compounds, pyrazolotriazoles, 5-pyrazolones, phenols, and naphthols, and these coupler residues contain ballast in the molecule. It may have a group. Examples of the above ballast group include an alkylacylamide group, an arylacylamide group, a succinimide group, and a phthalimide group, each of which may have a substituent, and in this case, the substituent has a carbon atom number of 12 Examples include the above-mentioned linear or branched alkyl groups, alkoxy groups, aryl groups, alkylacylamide groups, alkylsulfonamide groups, and the like. Furthermore, in the above general formula, the bond represented by B may be, for example, a monovalent linking group in which the above coupler residue and the residue of the dye or dye precursor are directly bonded, or a bond between both of the above residues. It may be a divalent linking group that indirectly links groups. As the divalent linking group used in the present invention, the following groups can be mentioned. (1)−OCH ₂ −

【formula】

【formula】

[Formula] (7)-S-

【formula】

[Formula] (8)−NH−

【formula】

(9)−NHSO ₂ −

【formula】

[Formula] (10)-N=N- (Here, R ₁ to _{R 6} represent an alkyl group, an aryl group, or an acyl group that may have a substituent) Furthermore, in the general formula, C represents Examples of dyes or dye precursor residues include monoazo dyes, azomethine dyes, indoaniline dyes,
Examples include bisazo dyes, anthraquinone dyes, triphenylmethane dyes, nitrodiphenylamine dyes, phthalocyanine dyes, and residues of these dye precursors. Specific compound examples of the dye or dye precursor residue represented by C in the general formula () are described below. (Exemplary compound) Yellow dye or its precursor In the above, R ₁ to _{R 6} are a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aryl group, an acylamino group, an acyl group, a cyano group, a hydroxyl group,
Alkylsulfonylamino group, arylsulfonylamino group, alkylsulfonyl group, hydroxyalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group, aryloxyalkyl group, nitro group, halogen atom, sulfamoyl group, N-substituted sulfamoyl group , carbamoyl group, N-substituted carbamoyl group,
Represents groups such as acyloxyalkyl groups, amino groups, substituted amino groups, alkylthio groups, and arylthio groups. Next, specific examples of the dye-forming substances represented by the general formula () used in the present invention will be listed, but the present invention is not limited to these. Furthermore, the dye-forming substance used in the present invention can be represented by the following general formula (). General formula () A-B-D In the formula, A and B represent the same groups as A and B in the general formula (), and D represents a ballast group. Moreover, B is bound to the active site of A. However, the coupler residue represented by A above preferably does not contain a ballast group in the molecule. The coupler residue represented by A, the bond represented by B, and the ballast group represented by D include those mentioned above. Typical specific examples of the dye-forming substance represented by the above general formula () are listed below, but the present invention is not limited thereto. The coating amount of the dye image-forming substance used in the present invention as listed above is 1×10 ^-5 to 1×10 ^-2 mol/
m ² , preferably 2×10 ⁻⁴ to 2×10 ⁻³ mol/m ² . There are various methods for adding these pigment-forming substances to the regions, but even if they are added uniformly to each region, they may be added unevenly to a part of each region, for example in the form of a stripe. May be added to. Particularly if the dye-forming substance is colored, a non-uniform addition method is preferred. The pigment-forming substance used in the present invention can be dispersed in a hydrophilic colloid carrier by various methods depending on the type of compound. For example, sulfo group,
A compound having a dissociable group such as 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-
Examples include n-butyl phthalate. Among these dispersing solvents, those with relatively low vapor pressures can be volatilized during drying of the photographic layer or used in U.S. patent applications prior to coating.
It can also be volatilized by the method described in No. 2322027 and No. 2801171. Among these dispersion solvents, those that are easily soluble in water are disclosed in U.S. Patent No.
It can be removed by a water washing method as described in No. 2949360 and No. 3396027. In order to stabilize the dispersion of the dye-forming substance and facilitate the process of dye image formation, it is advantageous to incorporate it with the dye-forming substance in the photographic element in a solvent that is substantially insoluble in water and has a boiling point above 200° C. at normal pressure. It is. Suitable high-boiling solvents for this purpose include triglycerides of higher fatty acids, aliphatic esters such as di-octyl adipate, phthalate esters such as di-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 substance in the photosensitive element to stabilize the dispersion of the dye-forming substance and facilitate the dye image formation process. Philic polymers suitable for this purpose include: sierrac; phenol-formaldehyde condensates; poly-n-butyl acrylate; copolymers of n-butyl acrylate and acrylic acid;
Examples include n-butyl acrylate and copolymers of styrene and methacramide. These polymers may be dissolved in an organic solution 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, a high-speed rotary mixer, a colloid mill, a high-pressure milk homogenizer, the high-pressure homogenizer disclosed in British Patent No. 1304264, an ultrasonic emulsifier, etc. are useful.
Dispersion of dye-forming substances is greatly aided by the use of surfactants as emulsion aids. Surfactants useful in dispersing the pigment-forming substances used in the present invention include sodium triisopropylnaphthalene sulfonate, sodium dinonylnaphthalene sulfonate, sodium p-dodecylbenzenesulfonate, and sodium dioctyl sulfosuccinate. There are salts, sodium cetyl sulfate, and anionic surfactants disclosed in Japanese Patent Publication No. 39-4293, and the combination of these anionic surfactants and higher fatty acid esters of anhydrohexitol is disclosed in U.S. Patent No. 3,676,141. Shows particularly good emulsifying ability as advertised. The photosensitive silver halide emulsion layer used in the present invention only needs to be sensitive to monochromatic light used for exposure, and may be composed of two or more different layers. . 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 is made of active gelatin, sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, selenium sensitizers, noble metal sensitizers, such as gold sensitizers, etc. Chemical sensitization can be carried out using sensitizers such as ruthenium, rhodium, iridium, etc. alone or in combination as appropriate. In the method of the present invention, it is preferable to use laser light, particularly semiconductor laser light, as the monochromatic light for exposure. Therefore, the silver halide emulsion layer used in the present invention is spectrally sensitized to a wide wavelength range, and preferably spectrally sensitized to an infrared wavelength range. Various sensitizing dyes are used for this purpose, and representative dyes include cyanine, merocyanine, trinuclear or tetranuclear cyanine, styryl, hemicyanine, oxonol, hemioxonol, and the like. Examples of cyanine dyes include thiazoline, oxazoline,
Preferably, those having a basic nucleus such as pyrroline, pyridine, oxazole, thiazole, selenazole, and imidazole include an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group, Alternatively, it may have an enamine group capable of forming a fused carbocyclic or heterocyclic ring.
Further, 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, merocyanine pigments have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolidinedione nucleus, barbituric acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. Good too. 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, typical sensitizing dyes with a maximum spectral sensitization wavelength suitable for spectral sensitization in the infrared wavelength region include:
12-acetoxy-3,3'-diethylthiatetracarbocyanine perchlorate, 12-acetoxy-
3,3'-diethylthiapentacarbocyanine perchlorate, 3,3'-diethyl-9,11-neopentylene thiatetracarbocyanine 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′-
dienyl}-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]thiazoliumio In addition, cyanines have 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-de-3-ethylbenzthiazolidenemethylidene)-5-cyclohexenylidenepentadienyl}-3-ethylbenzthiazolinium iodide, also 2-{5-( 3-ethylbenzthiazolinideneethylidene)-4-oxothiazolin-2-yl-propylidene}-3
-Ethylbenzthiazole, 3-(3-ethylbenzthiazolinylidene-butadienylidene)-6
-(3-ethyl-benzthiazolinylidenehexatrienylidene)-hexane-1,2,4,5-
Examples include tetraone. Also, many other cyanine, merocyanine, etc., and many other polynuclear dyes can be used. 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-pentadiol, esters of ethylene bisglycolic acid, bis-ethoxydiethylene glycol succinate, amides of acrylic acids, latex, etc. and formaldehyde, halogen-substituted fatty acids such as mucobromic acid, compounds with acid anhydride groups, dicarboxylic acid chlorides, biesters of methanesulfonic acid, and aldehyde groups with 2
Various photographic additives such as gelatin hardening agents such as sodium bisulfite derivatives of dialdehydes separated by trivalent carbon atoms, spreading agents such as saponins, or coating aids such as sulfosuccinates, etc. It can contain. 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 whitening agent, 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
Syariamyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dithyabutylphenyl)5-chlorobenzotriazole, 2-(3',5'-dithyabutylphenyl) -Shyabutyl-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-
Octylphenyl salicylate, 2,4-dita-
Various known compounds such as syabutylphenyl-3,5-dita-syabutyl-4-hydroxybenzoate can be used. 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,
Vinyl pyridine polymers disclosed in No. 2484430, No. 3148061, No. 3756814, etc.
and vinylpyridinium cationic polymer;
Polymers containing dialkylamino groups disclosed in 2675316; aminoguanidine derivatives disclosed in 2882156; 3625694, 3859096, 4128538, British Patent No.
Polymer mordants capable of crosslinking with gelatin etc. as disclosed in US Pat. No. 1277453, etc.;
Aqueous sol type mordant disclosed in the specifications of No. 3958995, No. 2721852, No. 2798063, etc.;
The water-insoluble mordant disclosed in No. 3898088;
No. 3642482, No. 3488706, No. 3557066, No. 3271147, No. 3271148, JP 50-71332
No. 53-30328, No. 52-155528, No. 53-125
No. 53-1024, No. 54-74430, No. 08 (Nippon Kayaku), High Bright 1001 (Dainichiseika), Uvitex CB
(Ciba-Geigy), Mikephore ETM (Mitsui Toatsu)
There are commercially available products such as 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 with nitrogen-containing heterocyclic moieties, polymers containing these quaternary cation groups, etc., and have a high molecular weight.
5000-200000, especially 10000-50000. For example, U.S. Patent No. 2548564, U.S. Patent No. 54-
Mordants disclosed in the specifications and publications of No. 124726, No. 55-22766, and No. 55-142339 can be mentioned. 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 value lowering substance reduces the PH value of the image receiving layer from about 13 or 14 to at least 11, preferably 5, within a short period of time after swelling.
It has the function of lowering it to ~8. For example, polymeric acids such as those disclosed in U.S. Pat. No. 3,862,819 or solid acids or metal salts such as those disclosed in U.S. Pat. No. 2,584,030 such as zinc acetate, zinc sulfate, magnesium acetate, etc. may be used. You can get good results. 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 (sometimes referred to as a spacer layer or "inert spacer layer"). Suitable materials for use in the neutralization layer and timing layer include Research Disclosure,
vol 123, paragraph 12331, July 1974 and vol 135,
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 Al _X As/GaAs (700 to 900 nm),
In _1-X GaxAsl−ypy/InP (900-1700nm), In _1-X
Examples include semiconductor lasers using materials such as GaxAsl-ySby/GaSb (1700 to 4000 nm). The semiconductor laser that can be used as a light source for exposing the photosensitive material of the present invention is a semiconductor laser that has an oscillation wavelength in the range of 600 to 1000 nm, and the semiconductor lasers that are currently commercialized have an oscillation wavelength of 700 to 1000 nm.
It is a semiconductor laser with an oscillation wavelength of . Further, other than these specific examples, any semiconductor laser having an oscillation wavelength of 600 to 1000 nm can be advantageously used in the photosensitive element according to the present invention. The developer used to develop the photosensitive silver halide layer in the method of the present invention is a color developing agent commonly used in color photography. For example, ``The Theory of the Photographic Process'' by T.H. James, Volume 4.
Examples include aminophenols, phenylenediamines, and hydrazones described in Chapter 11, Vol., (Macmillan, 1977). These color developing agents can be used as color developing agent precursors, and examples of the aforementioned precursors include U.S. Pat.
In addition to the Schiff-based color developing agent precursor described in No. 3342599, Japanese Patent Application Publication No. 54-9924, Research Disclosure No. 14850, No. 15159, U.S. Patent Nos. 169061 and 803783, etc. Imide-type precursors described, U.S. Pat.
No. 4060418, JP-A-52-97936, JP-A No. 53-135628
Urethane type precursor described in US Pat. No. 3,719,492, US Pat. No. 3,764,328
No. 56-6234, 56-54430, 56-
No. 59232, No. 56-67842, No. 56-81837, No. 56
−83734, No. 56-83735, No. 56-83736, No.
Salt-forming precursors described in No. 56-89735, etc.
Other US Patent No. 2695234, West German Patent No. 1159758
Other color developing agent precursors described in Research Disclosure, No. 1200679, Research Disclosure, No. 13924, and the like can be mentioned. 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. In a preferred embodiment of the invention, processing solution is absorbed into the exposed photosensitive element from a non-viscous processing solution, for example by passing the exposed photosensitive element through a container of processing solution. Other techniques can also be used that allow the small amounts of processing solution required to be applied virtually uniformly over the surface of the negative, such as 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 specialized 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 superposed 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 is also possible to include a reagent whose primary function is to facilitate adhesion to the substrate, 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 is a method of supplying with a brush or the like. For example, US Patent No. 3103153, US Patent No. 3112685, US Patent No.
3195435, 3626832, and 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 a dry image-receiving element 8 after the exposed photosensitive element 5 has been immersed in a container 7 of a non-viscous processing solution 6 for a certain period of time and then removed from the container 7.
9 and 10, thereby indicating that it is in front-to-front contact therewith. 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. 4223991. 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, it is desirable to use a light-shielding agent such as carbon black at appropriate locations on photographic elements having various layer configurations to shield 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. 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 and cellulose esters, such as cellulose triacetate and diacetate, polystyrene, polyamide, homo- and copolymers of vinyl chloride, poly(vinyl acetal), polycarbonate. , olefin alone −
and copolymers such as polyethylene and polypropylene, and dibasic aromatic carboxylic acids and 2
Polyesters with 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, the exemplified compound (6) of the present invention is added.
A 10% gelatin aqueous solution in which 4.9 g of 100% di-n-butyl phthalate was dissolved and dispersed in 5 g of di-n-butyl phthalate.
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 4.2 g of exemplified compound (3) was used instead of exemplified compound (6), 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 4.3 g of exemplified compound (7) was used instead of exemplified compound (6), and the irradiation angle of 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 liquid) Silver bromide emulsion Monodispersed octahedral emulsion with a particle size of 0.4 μm containing 0.353 mol of silver and 50 g of gelatin per 1 kg...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...15 ml Photosensitive element prepared as above In addition, a semiconductor laser printer (5mW.GaAlAs laser, oscillation wavelength
Exposure was performed at 780 nm). FIG. 10 shows a laser beam scanning optical system used in the above exposure. 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. Regarding the output control and modulation method of the semiconductor laser at this time, see Part 1.
1, 12 and 13. After exposure, the photosensitive element is immersed in a developer having the composition shown below for 20 seconds, and is superimposed on an image receiving element prepared by coating resin-coated paper with a coating solution having the composition shown below.
After being passed between the pressure rollers of the processor shown in the figure and left for 2 minutes, 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) Ethylenediaminetetraacetic acid, disodium salt
1.0g Sodium sulfite 2.0g Potassium bromide 0.5g Sodium carbonate monohydrate 42g 3-Methyl-4-amino-N-ethyl-N-
(β-Methanesulfonamidoethyl)-aniline sulfate 8.0g Add water to make 1. (Image-receiving layer coating liquid composition) Poly[styrene-co-N,N-dimethyl-N
-Benzyl-N-P-(methacryloylaminophenyl)methylammonium chloride-
Co-divinylbenzene 5.4g Gelatin 5.4g Tetrakis(vinylsulfonylmethyl)methane 0.07g Add water to make 200ml. A good yellow wedge image was obtained on the receiving element which was diffusely transferred from a photosensitive element exposed to 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 to 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 electric signals. Table 1 below shows the minimum and maximum densities of color images obtained on each of the above image receiving elements.

【table】

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. Example 2 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 undercoat layer, a 10% gelatin aqueous solution in which 4.9 g of the exemplary compound (49) of the present invention was dissolved in 5 g of di-n-butyl phthalate and dispersed for protection.
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. Indeed, on top of this first gelatin layer, a second gelatin layer was prepared in the same manner as above, except that 4.6 g of exemplified compound 36) was used instead of exemplified compound (49), and the irradiation angle of ultraviolet rays was changed. Created a gelatin layer. Further, a third gelatin layer was placed on the second gelatin layer in the same manner as above, except that 4.5 g of the exemplified compound (40) was used instead of the exemplified compound (49) and the irradiation angle of the ultraviolet rays was changed. A gelatin layer was created. A silver halide emulsion having the same composition as that shown in Example 1 was applied as a photosensitive layer on the striped filter layer thus obtained.
A light-sensitive element was obtained by coating the silver in an amount of 5.0 mg per cm ² . The photosensitive element prepared above was exposed to light using a semiconductor laser printer (5 mW. GaAlAs laser, oscillation wavelength: 780 nm) having a construction block as shown in FIG. 9, as an example. FIG. 10 shows a laser beam scanning optical system used in the above exposure. 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. Regarding the output control and modulation method of the semiconductor laser at this time, see Part 1.
1, 12 and 13. After exposure, the photosensitive element is immersed in a developer having the composition shown below for 20 seconds, and is superimposed on an image receiving element prepared by coating resin-coated paper with a coating solution having the composition shown below.
After being passed between the pressure rollers of the processor shown in the figure and left for 2 minutes, the photosensitive element and image receiving element were separated and the image receiving element was washed with a 0.5% acetic acid aqueous solution. 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 3 below shows the minimum and maximum densities of color images obtained on each of the above image receiving elements.

Table 4 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 3 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 4, 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. It can be understood that this proves that each region has the ability to uniformly receive the laser light and uniformly emit each colorant having different tones. Effects of the Invention According to the present invention, a high-quality color image 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 configuration of the photosensitive element according to the present invention, FIG. 3 is a configuration diagram of the same photosensitive element exposed to laser light, and FIG. 4 is a diagram showing the structure of the same photosensitive element after exposure. A cross-sectional view is shown when the dye is released and diffused from the photosensitive element and a color image is transferred to the image receiving element. FIG. 5 is a cross-sectional view of a photosensitive element showing still another embodiment of the present invention, and FIG. 6 is a top view showing the arrangement shape of the layers consisting of each area in both A and B.
Furthermore, FIG. 7 is a sectional view of a photosensitive element provided with a lenticular lens as yet another embodiment. FIG. 8 is a sectional view showing the configuration of a processor used in the method of the present invention. Figure 9 is a configuration block diagram of the laser printer, and Figure 10 shows the laser beam scanning optical system.
FIG. 1 shows an output control signal, FIG. 12 is a semiconductor laser output control block diagram, and FIG. 13 is a diagram showing pulse modulation of the semiconductor laser. DESCRIPTION OF SYMBOLS 1...Support, 2...Mosaic layer, 3...Photosensitive silver halide emulsion layer, 4...Image receiving element, 5...
Photosensitive element, 6...processing solution.

Claims (1)

[Scope of Claims] 1. A mosaic layer in which at least three types of pigment-forming substances capable of releasing pigments or their precursors having different tones are contained in different regions, and the regions are arranged in a striped or mosaic shape; A photosensitive element having a photosensitive silver halide emulsion layer that is sensitive to light in a photosensitive wavelength range of 600 nm or more is passed through the mosaic layer to form regions containing at least three types of dye-forming substances, each of which has a specific dye. A diffusible dye that can be exposed to imagewise light by exposing it to monochromatic light in at least three parts in accordance with the color image corresponding to the forming substance and contacting the oxidized product of the developer in the presence of a developer. or a method of forming a color image, which comprises generating a distribution of a diffusible dye precursor and diffusing and transferring at least a portion of the imagewise distribution onto an image-receiving element to form a color image on the image-receiving element. 2. The color image forming method according to claim 1, wherein the monochromatic light is laser light. 3. The color image forming method according to claim 2, wherein the laser light is a semiconductor laser light. 4. The color according to claim 1, wherein the dye-forming substance is a compound capable of reacting with an oxidized form of a silver halide developer to release a diffusible dye or a diffusible dye precursor. Image forming method. 5. The color image forming method according to claim 4, wherein the silver halide developer is a color developing agent selected from a p-phenylenediamine developer or a p-aminophenol developer. .