JP2649864B2 - Dye fixing element - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an image forming material, and more particularly to a dye fixing material having no coating unevenness and white spots.

(Background Art) The photographic method using silver halide is superior to other photographic methods, such as electrophotography and diazo photographic methods, in terms of photographic characteristics such as sensitivity and gradation control, and thus has been widely used in the past. Used.

In this photographic method, a light-sensitive element having a silver halide emulsion layer and a dye-fixing element having a dye-fixing layer are laminated, and an alkali-treating composition is developed in layers in the laminate, Is immersed in an alkaline processing liquid.

In recent years, when a photosensitive silver halide and / or an organic silver salt is reduced to silver by a thermal phenomenon, a diffusible dye is generated or released in response to or opposite to this reaction, and this diffusion is caused. A method of transferring a sexual dye to a dye-fixing element by a mordant has also been developed, for example, U.S. Pat.
No. 9, No. 4,474,867, No. 4,478,927, No. 4,507,3
No. 80, 4,500,626, 4,483,914, JP-A-58-
149046, 58-149047, 59-152440, 59-15
4445, 59-165054, 59-180548, 59-1684
No. 39, No. 59-174832, No. 59-174833, No. 59-174834
No. 59-174835, No. 62-65038, No. 61-23245,
These are described in European Patent Publications 210,660A2 and 220,746A2.

(Problems to be Solved by the Invention) However, in the dye-fixing element for fixing the dye using the mordant as described above, the coating unevenness of the dye-fixing layer due to the drying wind easily occurs, and therefore, the density unevenness of the output image tends to occur. There was a problem.

The present inventors used natural polymer polysaccharides derived from red algae, which are known to easily gel, in order to solve coating unevenness. As a result, although it was sufficient to improve the coating unevenness, there was a problem that white spots frequently occurred. Here, the white spot unevenness refers to a failure in which, when a dye image is transferred to a dye fixing element, a spot-like portion where the dye is not transferred is generated in a portion where the dye image should be transferred.

Accordingly, an object of the present invention is to provide a dye-fixing element having no coating unevenness and no white spots.

(Means for Solving the Problems) An object of the present invention is to provide a dye-fixing layer containing a mordant for fixing a movable dye imagewise distributed on a support and a layer containing at least a natural high molecular polysaccharide derived from red algae. Wherein the dye-fixing element has at least one layer comprising a mordant and a hydrophilic binder not containing the natural polymer polysaccharide, between the dye-fixing layer and the layer containing the natural polymer polysaccharide. Solved by the dye fixation element.

The dye-fixing element of the present invention is at least provided on a support, a dye-fixing layer containing a mordant, a layer containing a natural high-molecular polysaccharide derived from red algae, and an intermediate layer provided between both layers, This intermediate layer is a layer composed of a mordant and a hydrophilic binder not containing the natural high molecular polysaccharide. As the hydrophilic binder used for the intermediate layer, JP-A-62-253159
(26) to (28). Specifically, a transparent or translucent hydrophilic binder is preferable, for example, gelatin, a protein or cellulose derivative such as a gelatin derivative, starch, gum arabic,
Examples include natural compounds such as polysaccharides such as dextran and pullulan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, and other synthetic high molecular compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) can also be used. Two or more of these binders may be used in combination.

If necessary, other additives such as a surfactant, a thickener, and a matting agent may be added to the intermediate layer.

The coating amount of the hydrophilic binder in the intermediate layer can be arbitrarily determined, but is generally about 0.05 g to 10 g, preferably about 0.1 g to 1 g per 1 m ² of the support.

In the present invention, when viewed from the direction in which the pigment is diffused, it is preferable to arrange the pigment identification layer in the middle layer of the layer containing the natural high molecular polysaccharide derived from red algae.

The dye-fixing element may be coated separately on a support separate from the photosensitive element, or may be coated on the same support as the photosensitive element. As for the relationship between the photosensitive element and the dye-fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention.

The dye-fixing element may be provided with auxiliary layers such as a release layer, an anti-curl layer and an undercoat layer, if necessary.

As the natural high molecular polysaccharide derived from red algae used in the present invention, natural foods obtained by extracting and purifying from red algae described in Table 1 on page 21 of “Food Industry” Vol. 31 (1988) can be used. Molecular polysaccharides can be mentioned.

Natural polymer polysaccharides extracted and purified from red algae are often various mixtures. In the present invention, this mixture can be used as it is, or can be used as a simpler substance having higher purity. Among the natural high molecular polysaccharides derived from red algae used in the present invention, particularly suitable for the present invention are agar, copper carrageenan, lambda carrageenan, iota carrageenan, furceleran and the like. These substances are commercially available. For example, copper carrageenan can be obtained as Taito gelling agent NK-4 manufactured by Taisu Co., Ltd. A mixture of lambda carrageenan and a trace amount of copper carrageenan can be obtained as Taito gelling agent MV manufactured by Taisu Corporation. The amount of natural polymer polysaccharide derived from red algae of the present invention can be arbitrarily set, the support 1 m ² per
0.005 to 10 g / m ² , particularly about 0.01 to 4 g / m ² is suitable.

The mordant of the present invention can be arbitrarily selected from commonly used mordants, and among them, a polymer mordant is particularly preferable. Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, and a polymer containing these quaternary cationic groups.

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary amino group include the following. The numbers of the monomer units represent mol% (the same applies hereinafter).

Such.

Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group include U.S. Patent Nos. 4,282,305, 4,115,124, and 3,148,061.
No., JP-A-60-118834, JP-A-60-1222941, JP-A-62
The following may be mentioned, including the mordants described in JP 244043 and JP-A-62-244036.

Such.

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101, 2,093,041, and 1,1.
No. 594,961, U.S. Pat.Nos. 4,124,386 and 4,115,124
No. 4,273,853, No. 4,450,224, JP-A-48-28
The following may be mentioned, including the mordants described in No. 325 and the like.

Such.

In addition, preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary ammonium salt include U.S. Patent Nos. 3,709,690 and 3,898,088,
No. 3,958,995, JP-A-60-57836, JP-A-60-60643
And mordants described in JP-A Nos. 60-122940, 60-122942, 60-235134 and the like.

Such.

In addition, U.S. Patent Nos. 2,548,564 and 2,484,430,
Nos. 3,148,151 and 3,756,814, vinyl pyridine polymer and vinyl pyridinium cationic polymer disclosed in U.S. Pat.
3,859,096, 4,128,538, UK Patent 1,277,453
No. 3,958,995, US Pat. No. 2,721,852
No. 2,798,063, JP-A-54-115228, JP-A-54-145
No. 529, No. 54-26027, aqueous sol type mordant disclosed in U.S. Pat. No. 3,898,088; water-insoluble mordant disclosed in U.S. Pat. No. 3,898,088; U.S. Pat. ) Reactive mordants capable of forming a covalent bond with the dyes disclosed in the specification; and US Pat. No. 3,709,
No. 690, No. 3,788,855, No. 3,642,482, No. 3,48
No. 8,706, No. 3,557,066, No. 3,271,147, No. 3,2
No. 71,148, JP-A-50-71332, JP-A-53-30328, JP-A-52-30
Examples include mordants disclosed in the specifications of 155528, 53-125 and 53-1024.

Other examples include mordants described in U.S. Pat. Nos. 2,675,316 and 2,882,156.

The molecular weight of the polymer mordant of the present invention is 1,000 to 1,000,000
Is suitable, and particularly preferably 10,000 to 200,000.

The light-sensitive element of the present invention basically has a light-sensitive silver halide, a binder and a dye-donating compound on a support, and may further contain other additives as necessary. These components are often added to the same layer, but may be added separately to another layer if they can react. For example, if a dye-donating compound which is colored is present in the lower layer of the silver halide emulsion, it prevents the sensitivity from lowering. In the case of the thermal phenomenon method, the reducing agent or its precursor is preferably incorporated in the photosensitive element,
For example, it may be supplied from outside by a method such as diffusion from a dye fixing element described later.

The amount of the reducing agent or its precursor to be used is preferably from 0.001 to 20 mol, particularly preferably from 0.01 to 10 mol, per mol of silver halide.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers sensitive to different spectral regions are used in combination. For example, blue layer, green layer,
There are a combination of three red-sensitive layers, a combination of green-sensitive layers, red-sensitive layers, and infrared-sensitive layers. Each light-sensitive layer can adopt various arrangement orders known for conventional color light-sensitive elements. Each of these photosensitive layers may be divided into two or more layers as necessary. For example, each photosensitive layer is composed of two layers of a high sensitivity layer and a low sensitivity layer, or three layers of a high sensitivity layer, a middle sensitivity layer and a low sensitivity layer.

The photosensitive element can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a back layer.

The silver halide that can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide.

The silver halide emulsifier used in the present invention may be a surface latent image type agent or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion having a different phase between the inside of the grain and the grain surface layer may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used.

The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habit of the silver halide grains may be any of cubic, octahedral, tetrahedral, high aspect ratio tabular, and the like.

Specifically, U.S. Patent No.4,500,626, column 50, 4,62
And silver halide additives described in Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1978), JP-A-62-253159, and the like.

The silver halide emulsion may be used as it is after unripe, but usually it is used after chemical sensitization. Known emulsion sensitization methods, reduction sensitization methods, noble metal sensitization methods, and the like can be used alone or in combination for emulsions for conventional light-sensitive elements. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

The coating amount of the silver under the photosensitive halogen used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

Silver halide used in the present invention, methine dyes,
Alternatively, spectral sensitization may be performed. Dyes used include cyanine dyes, merocyanine dyes, mixed cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, U.S. Pat.No. 4,617,257, JP-A-59-180
No. 550, No. 60-140335, RD17029 (1978), pp. 12-13, and the like.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for supersensitization.

Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641). And those described in Japanese Patent Application No. 61-226294).

These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or may be added to U.S. Pat.
No. 4,225,666, before and after nucleation of silver halide grains. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

In the thermal phenomenon method, together with the photosensitive silver halide,
An organic metal salt can be used in combination as an oxidizing agent. Among such organic metal salts, an organic silver salt is particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in U.S. Pat. No. 4,500,626, columns 52-53. Also useful are silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235 and acetylene silver described in JP-A-61-249044. Two or more organic silver salts may be used in combination.

The above organic silver salts can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of the photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants or photographic stabilizers can be used. An example is RD17643
(1978) Azoles and azaindenes described on pages 24 to 25, carboxylic acids and phosphoric acids containing nitrogen described in JP-A-59-168442, or mercapto compounds and metals thereof described in JP-A-59-111636 Salts and acetylene compounds described in JP-A-62-87957 are used.

First, examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Also,
A 2-equivalent coupler which has a diffusion-resistant group as a leaving group and forms a diffusible dye by an oxidative coupling reaction is also preferable. Specific examples of developing agents and couplers can be found in James, "The Theory of the Photographic Processes," 4th Edition.
s ") Pages 291-334 and 354-361, JP-A-58-123533.
No. 58-149046, No. 58-149047, No. 59-111148
Nos. 59-124399, 59-174835, 59-231539
No. 59-231540, No. 60-2950, No. 60-2951, No.
No. 60-14242, No. 60-23474, No. 60-66249, No. 5
The details are described in, for example, JP-A-2-24849 and JP-A-53-129036.

Further, as another example of the dye-donating compound, a compound having a function of releasing or diffusing a diffusible dye imagewise can be mentioned. This type of compound can be represented by the following general formula [LI].

(Dye-Y) _n -Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents a latent image in an image form. (Dye-Y) _n -Z corresponding to or opposite to the photosensitive silver salt having the formula (1), or it releases Dye, and the released Dye and (Dye- Y) represents a group having a property that causes a difference in diffusivity between _n- Z, and _n represents 1 or 2, and when n is 2, two Dye-Ys are the same but different. Is also good.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds. The following (1) to (3) are for forming a diffusible dye image (positive dye image) in reverse correspondence to the phenomenon of silver halide, and "(1)" is for forming a diffusible dye image (positive dye image) in response to the silver halide phenomenon. (A negative dye image).

U.S. Pat.Nos. 3,134,764, 3,362,819, 3,591
No. 7,200, No. 3,544,545, No. 3,482,972, and the like, dye developing agents in which a hydroquinone-based developing agent and a dye component are linked can be used. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide.

As described in U.S. Pat. No. 4,503,137, non-diffusible compounds which release diffusible dyes in an alkaline environment but lose their ability to react with silver halide can also be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat.No. 3,980,479 and the like, and an intramolecular reversion reaction of an isoxazolone ring described in U.S. Pat. Compounds that release diffusible dyes are included.

As described in U.S. Pat.No. 4,559,290, European Patent No. 220,746A2, Published Technical Report 87-6199, etc., a non-diffusible substance which reacts with a reducing agent remaining unoxidized due to a phenomenon to release a diffusible dye Can also be used.

Examples are U.S. Pat.Nos. 4,139,389 and 4,13
No. 9,379, JP-A-59-185333, compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in U.S. Pat.
No., JP-A-59-101649, JP-A-61-88257, RD24025 (19
1984) and the like, which release a diffusible dye by an electron transfer reaction in the molecule after being reduced, West German Patent No. 3,
008,588A, JP-A-56-142530, U.S. Pat.
No. 3,619,884, etc., compounds that release a diffusible dye by cleavage of a single bond after reduction, and nitro, which releases a diffusible dye after electron acceptance described in U.S. Pat.No. 4,450,223, etc. And compounds which release a diffusible dye after electron acceptance as described in U.S. Pat. No. 4,609,610.

Also, more preferably, EP 220,74
6A2, Published Technical Report 88-6199, Japanese Patent Application No. 62-34953, 62-349
Compounds having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in No. 34954, etc., in one molecule described in Japanese Patent Application No. 62-106885. To SO
_2- X (X is as defined above) and a compound having an electron-withdrawing group. A PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in Japanese Patent Application No. 62-106895. A compound having
Japanese Patent Application No. 62-1006887 discloses a compound having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule.

Among them, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. A specific example is European Patent No. 22
Compounds (1) to (3) and (7) described in No. 0,746A2
~ (10), (12), (13), (15), (23) ~ (26),
(31), (32), (35), (36), (40), (41),
(44), (53)-(59), (64), (70), Published Technical Report 87
-6199 compounds (11) to (23).

Compounds that have a diffusible dye as a leaving group and release a diffusible dye upon reaction with an oxidized reducing agent (DD
R coupler) can be used. Specifically, British Patent Nos. 1,3
No. 30,524, JP-B-48-39165, U.S. Pat.No. 3,443,940
And Nos. 4,474,867 and 4,483,914.

Is reducible to silver halides or organic silver salts,
A compound that releases a diffusible dye when the partner is reduced (DRR compound) can be used. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. A typical example is U.S. Patent No.
No. 3,928,312, No. 4,053,312, No. 4,055,428, No. 4,336,322, JP-A-59-65839, No. 59-69839,
Nos. 53-3819, 51-104343, RD17465, U.S. Pat.Nos. 3,725,062, 3,728,113, 3,443,939,
JP-A-58-116537, JP-A-57-179840, U.S. Pat.
No. 0,626. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, compounds (1) to (3) described in the above-mentioned U.S. Pat. (10)-(13),
(16)-(19), (28)-(30), (33)-(35),
(38) to (40) and (42) to (64) are preferred. Also useful are the compounds of U.S. Pat. No. 4,639,408, columns 37-39.

Other examples of the above-mentioned couplers and dye-donating compounds other than the general formula [LI] include dye silver compounds in which an organic silver salt is combined with a dye (Research Disclosure Magazine, May 1978, pp. 54-58, etc.); Azo dyes used in the heat developing silver dye bleaching method (US Pat. No. 4,235,957, Research Disclosure, April 1976, pp. 30-32, etc.), leuco dyes (US Pat. Nos. 3,985,565, 4,022,617, etc.) )
Etc. can also be used.

The above-mentioned hydrophobic additives such as the dye-donating compound and the diffusion-resistant reducing agent can be introduced into the layer of the photosensitive element or the dye-fixing element by a known method such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-8315
Nos. 4, 59-178451, 59-178452, 59-178453
No. 59-178454, No. 59-178455, High boiling organic solvents such as those described in No. 59-178457, etc., if necessary, as a low boiling organic solvent having a boiling point of 50 ° C. to 160 ° C. , Can be used.

The amount of the high boiling organic solvent is 1 g
10 g or less, preferably 5 g or less. Also, 1 cc or less per gram of binder, further 0.5 cc or less, especially
0.3cc or less is appropriate.

A dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method.

When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59
The surfactants listed on pages (37) to (38) of No. 157636 can be used.

In the present invention, a compound for stabilizing an image simultaneously with activation of development can be used in the photosensitive element. Specific compounds preferably used are described in U.S. Pat.
No. 626, columns 51-52.

As the reducing agent, those known in the field of silver halide photosensitive materials can be used.

Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used.

Examples of the reducing agent used in the present invention include inorganic reducing agents such as sodium sulfite and sodium hydrogen sulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazines, borane-amine complexes, hydroquinones, aminophenols Catechols, p-phenylenediamines, 3-pyrazolidones, hydroxytetronic acid, ascorbic acid, 4-amino-5-pyrazolones and the like.

More specifically, U.S. Patent No.
No. 4,483,914 No. 30-31, No. 4,330,617,
No. 4,590,152 and JP-A-60-140335, Nos. (17) to (1).
8), p. 57-40245, p. 56-138736, p. 59-178458
Nos. 59-53831, 59-182449, 59-182450
Nos. 60-119555 and 60-128436 to 60-128439
No. 60-198540, No. 60-181742, No. 61-2592
No. 53, No. 62-244044, No. 62-131253 to No. 62-1312
Up to 56, there are reducing agents and reducing agent precursors described on pages 78 to 96 of EP 220,746 A2.

Combinations of various reducing agents can also be used, such as those disclosed in U.S. Pat. No. 3,039,869.

If a diffusion resistant perfecting agent is used, an electron transfer agent and / or an electron transfer agent may be optionally added to facilitate electron transfer between the diffusion resistant reducing agent and the developable silver halide. Precursors can be used in combination.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors.
It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one that does not substantially move in the layer of the photosensitive element among the reducing agents described above, and is preferably a hydroquinone, Sulfonamidophenols, sulfonamidonaphthols, compounds described as electron donors in JP-A-53-110827, and non-diffusible dye-donating compounds having a reducing agent described below.

As the dye-providing compound having reducing properties, a dye developer described below, a compound described in U.S. Pat.No. 4,503,137, which releases a diffusible dye under an alkaline environment but loses its ability when reacted with silver halide, DRR compounds and the like.

Antioxidants include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols, hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes , Aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of these compounds.

Examples of color mixing inhibitors include hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives,
Chole derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenol derivatives and the like.

Oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, azo dyes are preferably used as filter dyes or irradiation or antihalation dyes.Other than these, cyanine dyes, azomethine dyes, triarylmethane dyes, Phthalocyanine dyes are also useful.

As developing bath preparations, antifoggants, and photographic stabilizers, azoles such as benzothiazolium salts, nitroimidazoles, nitromebenzimidazoles, sulobenzimidazoles, belomobenzimidazoles, mercaptothiazoles, and mercapto Benzothiazoles, mercaptobenzimidazole, mercaptothiadiazoles, aminotriazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Tetraazaindenes), pentaazaindenes and the like; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide and the like.

As the fluorescent bleach, K. Veenkataraman ed. “The Chemist
ry of Synthtic Dyes ", Vol. V, Chapter 8. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazoline compounds, naphthalimide compounds, and pyrazolines can be used. Compounds, carbostyryl compounds and the like.

As anti-fading agents other than antioxidants, (bissalicylaldoximato) nickel complexes and (bis-N, N-
Metal complexes typified by dialkyldithiocarbamato) nickel complexes (U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3-36, 4,254,195, columns 3-8, JP-A-50-8)
Nos. 7649, 62-174711, 61-88256 (27)-(2
9), benzotriazole-based compounds (US Pat. No. 3,533,794, etc.), 4-thiazolidone-based compounds (US Pat. No. 3,352,681, etc.), and compounds described in Japanese Patent Application Nos. 62-234103 and 62-31096. ) Benzophenone compounds (JP-A-46-2784, etc.) and other JP-A-54-48535
Nos. 62-136641 and 61-88256, JP-A-62-260115
There is an ultraviolet absorber described in No. 2, etc.

As a development terminator, a compound that neutralizes a base or reacts with a base to reduce the concentration of the base in the film and stop the development immediately after proper development, or a compound that suppresses development by interacting with silver and a silver salt is used. is there.

This is often used in the thermal development method, and specifically, an acid precursor that releases an acid upon heating, an electrophilic compound that causes a substitution reaction with a coexisting base upon heating, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. Body and the like.

Further details are described in JP-A-62-253159, pages (31) to (32).

A hydrophilic binder is preferably used for the constituent layer of the photosensitive element.

Examples thereof are described in JP-A-62-253159, page (26).
(28) those described on page 28. In particular,
There are those mentioned as binders for the intermediate layer of the dye fixing element.

When a system that performs a thermal phenomenon by supplying a small amount of water is used, the use of the above superabsorbent polymer makes it possible to quickly absorb water. Further, when the superabsorbent polymer is used for the dye fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye fixing element to another after transfer.

In the present invention, the coating amount of the binder is 1 m ² per 20g
The following is preferred, and the amount is particularly preferably 10 g or less, more preferably 7 g or less.

Examples of the hardener used in the constituent layers of the photosensitive element and the dye-fixing element include U.S. Pat.
No. 5, 62-245261, 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners Vinyl sulfone hardeners (such as N, N'-ethylene-bis (vinylsulfonylacetamide) ethane), N-methylol hardeners (such as dimethylol urea), or polymer hardeners (Japanese Patent Laid-Open No. Sho 62) -234157, etc.).

In the present invention, an image formation accelerator can be used in the photosensitive element and / or the dye fixing element.

Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the formation of a dye from a dye-providing substance or the decomposition of a dye or the release of a diffusible dye, and the photosensitive element layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. These details are described in U.S. Pat. No. 4,678,739, columns 38-40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are described in U.S. Pat.
2-65038.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in a dye-fixing element from the viewpoint of improving the storage stability of the photosensitive element.

In addition to the above, a combination of a sparingly soluble metal compound described in European Patent Publication No. 210,660 and a compound capable of forming a complex with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound); Compounds that generate a base by electrolysis described in JP-A 61-232451 can also be used as the base precursor.

In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

In the constituent layers of the photosensitive element and the dye fixing element, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, promoting development, and the like. Specific examples of the surfactant are described in JP-A Nos. 62-173463 and 62-183457.

The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17, JP-A-61-20944.
No. 62-135826 and hydrophobic surfactants such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluorinated ethylene resin. Can be

A matting agent can be used for the photosensitive element and the dye fixing element. Examples of the matting agent include compounds described in JP-A-61-88256, page (29), such as silicon dioxide, polyolefin and polymethacrylate, and benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like. Nos. 110064 and 62-110065.

In addition, the constituent layers of the photosensitive element and the dye fixing element include:
A heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like may be included. Specific examples of these additives are disclosed in
No. 88256, pages (26) to (32).

As the support of the photosensitive element or the dye fixing element, a support that can withstand the processing temperature is used. In general,
Paper and synthetic polymers (films). Specifically, polyethylene terephthalate, polycarbonate,
Synthesis of polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (eg, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, and film-processed synthetic paper made of polypropylene, etc., and synthesis of polyethylene, etc. Mixed paper made from resin pulp and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used.

These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used.

A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports.

The method of exposing and recording an image on a photosensitive element includes, for example, a method of directly photographing a landscape or a person using a camera, a method of exposing through a reversal film or a negative film using a printer or a enlarger, and a method of using a copier. Scanning and exposing the original image through slits using an exposure device, etc., exposing the image information by emitting light from a light emitting diode or various lasers via electrical signals, CRT, liquid crystal display, electroluminescence display And a method of outputting the image to an image display device such as a plasma display and exposing the image directly or via an optical system.

As the light source for recording an image on the photosensitive element, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a U.S. Pat.
The light sources described in the column can be used.

The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standard (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. Signals, image signals created using a computer represented by CG and CAD can be used.

The image forming method of the present invention includes a method of forming a diffusible dye image by thermal development, and diffusing and transferring this to a dye fixing element to form an image.

In this case, various steps can be combined.
For example, in the case of using a so-called two-sheet type photographic element in which a photosensitive layer and a dye fixing layer are formed on separate supports, (i) exposure step-heat development step-photosensitizer and dye fixing element (Ii) exposure step-superposition step of photosensitive element and dye fixing element-thermal development / transfer step-release step (iii) exposure step-thermal development step-solvent application step -Superposition step of photosensitive element and dye fixing element-transfer step-peeling step (iv) exposure step-solvent application step-superposition step of photosensitive element and dye fixing element-thermal development / transfer step-peeling step. be able to. The peeling step may be omitted depending on the configuration of the dye fixing element.

The above process is a convenient classification, and there is a case where a plurality of processes are continuously performed, for example, a case in which thermal development is performed following exposure, and a case where one process is performed in a plurality of stages. Includes cases that are not classified as Which combination of steps is selected depends on the method of generating a base, for example, by incorporating a pyrolytic base precursor, or by generating a base by reacting a compound contained in two photographic elements in the presence of a solvent. It can be selected, and also can be selected depending on the use of an accelerator for controlling the speed of development transfer.

The heating temperature in the heat development step is about 50 ° C. to about 25 ° C., but about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the latter case, the heating temperature in the transfer step is such that the transfer can be performed in the range from the temperature in the heat development step to room temperature, but it is particularly preferable that the heating temperature is 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Dye transfer is caused only by heat, but a solvent may be used to promote dye transfer.

Further, as described in JP-A-59-218443, JP-A-61-238056, etc., a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. It is. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower.
100 ° C or less is desirable.

Examples of the solvent used for promoting development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include Those described in the section of the formation accelerator are used. In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a soluble metal salt and a complex-forming compound may be contained in the solvent.

These solvents can be used in a method for imparting to the dye fixing element, the photosensitive element, or both. The amount used may be as small as not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, for example, there is a method described in JP-A-61-147244, page (26). Further, the solvent can be used by being previously incorporated in the photosensitive element or the dye fixing element or both in the form of enclosing the solvent in microcapsules.

In order to promote dye transfer, a method in which a hydrophilic thermal solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the photosensitive element or the dye fixing element can be adopted. The hydrophilic heat solvent may be incorporated in any of the photosensitive element and the dye fixing element,
It may be built in both. Also, the layer to be incorporated is an emulsion layer,
Any of an intermediate layer, a protective layer, and a dye-fixing layer may be used, but it is preferable to be incorporated in the dye-fixing layer and / or a layer adjacent thereto.

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alkenyls,
There are oximes and other heterocycles.

Further, in order to promote dye transfer, a high boiling organic solvent may be contained in the photosensitive element and / or the dye fixing element.

As a heating method in the development and / or transfer step, it is contacted with a heated block or plate, or in contact with a hot plate, hot presser, heat roller, halogen lamp heater, infrared and far infrared lamp heater, For example, passing through a high temperature atmosphere. Further, a resistive heating element layer may be provided on the photosensitive element or the dye fixing element, and the layer may be heated by being energized.

As the heating element layer, those described in JP-A-61-145544 can be used.

The method described in JP-A-61-147244, page (27) can be applied as a pressure condition and a method of applying pressure when the photosensitive element and the dye-fixing element are overlapped and brought into close contact with each other.

Any of a variety of thermal development equipment can be used to process the photographic elements of the present invention. For example, JP-A-59-75247, JP-A-59-75247
-17747, 59-181353, 60-18951, Shokai 6
An apparatus described in, for example, No. 2-25944 is preferably used.

The image forming method of the present invention also includes a so-called wet color diffusion transfer method in which a developing solution is used at around room temperature using a processing solution for development.

This wet color diffusion transfer method is described, for example, in Belgian Patent No. 757,959. Examples of the dye-donating compound that can be used in the wet color diffusion transfer method include the compounds represented by the aforementioned general formula [LI].

The photographic element used in the color diffusion transfer method will be described in more detail below.

The photographic element in this case is preferably a film unit in which a light-sensitive element and a dye-fixing element are combined.

In a typical form of the film unit, the dye fixing element and the photosensitive element are laminated on one transparent support, and after the transfer image is completed, it is necessary to peel the photosensitive element from the dye fixing element. There is no form. More specifically, the dye-fixing element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer, A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye-donating compound, magenta The dye-donating compound and the cyan dye-donating compound are respectively combined (here, “infrared-sensitive emulsion layer”
An emulsion layer having sensitivity to light of 0 nm or more, particularly 740 nm or more). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the dye-donating compound-containing layer so that the transferred image can be viewed through the transparent support. A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development processing can be completed in a light place. If desired, a release layer may be provided at an appropriate position so that all or a part of the photosensitive element can be released from the dye fixing element (for example, JP-A-56-67840 and Canada). Patent No. 674,082).

Further, in a separate form that does not require peeling, the photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and a dye fixing element is further laminated thereon.
A dye-fixing element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support, and an embodiment in which the photosensitive element is intentionally peeled from the dye-fixing element is described in U.S. Pat.
No. 718. On the other hand, there are roughly two typical forms in which a light-sensitive element and a dye-fixing element are separately coated on two supports, respectively, one of which is a peelable type and the other is a peelable type. More specifically, in a preferred embodiment of the peelable film unit, a light reflecting layer is provided on the back surface of the support, and at least one dye fixing layer is provided on the surface. The photosensitive element is coated on a support having a light-shielding layer. Before the end of the exposure, the coated layer of the photosensitive layer and the surface of the mordant layer are not facing each other, but after the end of the exposure (for example, during the developing process), Is turned upside down and overlaps with the dye fixing layer application surface. After the transfer image is completed in the mordant layer, the photosensitive element is immediately separated from the dye fixing element.

Further, in a preferred form of the peeling-free film unit, at least one mordant layer is applied on a transparent support, and the photosensitive element is coated on a support having a transparent or light-shielding layer, The photosensitive layer application surface and the mordant layer application surface face each other and are superimposed.

The photographic element of the wet color diffusion transfer system described above may further be combined with a container (processing element) that can be ruptured under pressure containing an alkaline processing liquid. Particularly, in a peeling-free film unit in which a dye fixing element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. In the case where the photosensitive element and the dye-fixing element are separately coated on the two supports, it is preferable that the processing element is arranged between the photosensitive element and the dye-fixing element at the latest at the time of development processing. Processing elements include light-blocking agents (carbon black) and
It is preferable to include a dye that changes its color depending on pH) and / or a white pigment (titanium oxide). Further, in the wet color diffusion transfer type film unit, a neutralization timing function comprising a combination of a neutralization layer and a neutralization timing layer is incorporated in a cover sheet, a dye fixing element, or a photosensitive element. preferable.

Hereinafter, specific examples will be described, but the present invention is not limited to these examples.

Example 1 A method for manufacturing a photosensitive element will be described.

Photosensitive silver halide emulsion (for red-sensitive emulsion layer) Well-stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide, 6 g of sodium chloride, and 30 mg of the following chemical A were added to 800 ml of water and kept at 50 ° C) ), The following solutions (I) and (II) were simultaneously added at an equal flow rate over 30 minutes. Thereafter, the following solution (III) and solution (IV) are simultaneously
Added over 0 minutes. Three minutes after the start of the addition of the solutions (III) and (IV), a solution of a mixture of the following dyes was added.

After washing with water and desalting, lime treatment, 22 g of ossein gelatin were added to adjust the pH to 6.2 and the pAg to 7.7, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazain Optimum chemical sensitization was performed at 60 ° C by adding den and chloroauric acid. Thus, a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.38 μ was obtained. The yield was 635 g.

Photosensitive layer Silver halide emulsion (for green photosensitive layer) Well-stirred aqueous solution (gelatin 20g, potassium bromide 0.30g, sodium chloride 6g and chemical A 0.015g in 730ml of water)
And the mixture was kept at 60.0 ° C) and the following solution (I) and (I
I) The solution was added simultaneously over 30 minutes. Next, the solution (III) and the solution (IV) were added for 30 minutes, and one minute after the completion of the addition, the following sensitizing dye solution was added.

After washing with water and desalting, add 20 g of gelatin, and optimally sensitize with pH adjusted triethylthiourea, chloroauric acid, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. did.

The resulting emulsion was a monodisperse cubic emulsion with an average grain size of 0.4μ, ending in 630g.

Photosensitive silver halide emulsion (for blue light-sensitive layer) Aqueous gelatin solution (20 g of gelatin, 3 g of potassium bromide, 0.03 g of the following chemical, and HO (CH ₂ ) ₂ S (CH ₂ ) _{2 in} 800 ml of water Add 0.25 g of S (CH ₂ ) ₂ OH and add 50 ° C
Solution (I) and solution (II) at the same time
It was added over a minute. Thereafter, the following solution (III) and (I
V) Solution was added simultaneously over 20 minutes. After the completion of the addition of the solution (III), a solution of the following sensitizing dye was added from 5 minutes.

After washing and desalting, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and the pAg to 8.5, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added. And metal chloride was added for optimal chemical sensitization. In this way, 600 g of a monodispersed tetrahedral silver iodobromide emulsion having an average grain size of 0.40 μm was obtained.

A method for preparing a dispersion of zinc hydroxide will be described. Average particle size 0.2μ zinc hydroxide 12.5g, carboxymethyl cellulose 1g as dispersant, sodium polyacrylate 0.1g
Was added to 100 ml of a 4% aqueous gelatin solution. This was crushed with a mill using glass beads having an average particle diameter of 0.75 mm for 30 minutes, and then the glass beads were separated to obtain a dispersion of zinc hydroxide.

 A method for preparing a dispersion of activated carbon will be described.

Activated carbon powder (reagent, special grade) manufactured by Wako Pure Chemical Industries, Ltd.
2.5g, Demol N1g manufactured by Kao Soap Co., Ltd. as dispersant, polyethylene glycol nonyl phenyl ether 0.25g
Was added to 100 ml of a 5% aqueous gelatin solution, and ground in a mill for 120 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a dispersion of activated carbon having an average particle size of 0.5 μm.

A method for preparing a dispersion of an electron transfer agent will be described. 10 g of the following electron transfer agent, 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5 g of the following anionic surfactant were added to a 5% aqueous gelatin solution, and the mixture was milled using glass beads having an average particle size of 0.75 mm. Milled for minutes. The glass beads were separated to obtain a dispersion of an electron transfer agent having an average particle size of 0.4 μm.

Electron transfer agent Anionic surfactant A method of preparing a gelatin dispersion of a dye-providing compound will be described.

Each of yellow, magenta, and cyan was weighed according to the formulation shown in the following table, and each was heated and dissolved at about 60 ° C. to form a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-processed gelatin, 0.6 g of sodium dodecylbenzenesulfonate and 50 ml of water were stirred and mixed, and then mixed with a homogenizer for 10 minutes.
Dispersed at 10,000 rpm. These dispersions are called gelatin dispersions of yellow, magenta and cyan dye-donating compounds.

Next, a method for preparing a gelatin dispersion of an electron donor for the intermediate layer will be described.

The following electron donor 23.6 g and the above high boiling solvent 8.5 g
Was added to 30 ml of ethyl acetate and dissolved by heating at 60 ° C. to obtain a uniform solution. This solution and a 10% aqueous solution of lime-processed gelatin 100
g, 0.25 g of sodium bisulfite, 0.3 g of sodium dodecylbenzenesulfonate, and 30 ml of water were stirred and mixed, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called a gelatin dispersion of an electron donor.

Dye-donating compound (1) Yellow dye-donating compound (2) Magenta dye donating compound (3) Cyan dye donating compound Electron donor High boiling point solvent Electron transfer agent precursor Electron donor Next, how to make a dye fixing element will be described.

As shown in the following table, a dye-fixing element (1) in which a coating layer having the first to third layers was applied on a support (1) on which a first layer and a second layer of a back layer had been applied in advance. Was.

The thickness of the coating solution from the first layer to the third layer was 12
Coating was carried out by the simultaneous multi-layer coating method as ml / m ² , 35 ml / m ² , and 15 ml / m ² .

After application, a cooling zone of 20 ° C is provided for 10m, 35 ° C, 35% RH
The drying was carried out with a drying air.

Next, a dye-fixing element (2) was prepared in exactly the same manner except that 0.06 g / m ² of copper carrageenan in the third layer of the dye-fixing element (1) was added.

Further, as shown in the following table, a dye-fixing element (3) was prepared by further adding one layer.

In addition, the thickness of the coating liquid from the first layer to the fourth layer is respectively set.
Coating was performed by a simultaneous multi-layer coating method at 6 ml / m ² , 35 ml / m ² , 6 ml / m ² , and 15 ml / m ² .

After application, a cooling zone of 20 ° C is provided for 10m, 35 ° C, 35% RH
The drying was carried out with a drying air.

The following processing was performed using the above photosensitive element and dye fixing element.

That is, the photosensitive element 101 was exposed to tungsten light at 5000 lux for 1/10 second through a gray filter.

Next, while supplying the exposed photosensitive element at a linear velocity of 20 m / sec, water of 15 ml / m ³ was supplied to the emulsion surface by a wire bar, and immediately thereafter, the dye fixing elements (1) to (3) and the film were fixed. They were overlapped so that the faces touched. The temperature of the absorbed membrane surface is 85
Heating was performed for 15 seconds using a heat roller whose temperature was adjusted to ° C., and peeled off from the dye-fixing element, a clear gray image was obtained on the dye-fixing element.

The obtained image corresponds to the air volume unevenness of the application drying air,
Density unevenness of 5 mm pitch occurred in parallel with the coating direction.

The following table shows the results of measuring the density unevenness of the gray part where the average density of each of Y (yellow), Y (magenta) and Cy (cyan) is 1.0 by micron densitometry (beam diameter 2 mm).

Further, the number of white spots having a diameter of 3 mm or more generated in the image is shown.

As is clear from the above table, according to the present invention, in the dye-fixing element having a dye-fixing layer containing a mordant and a layer containing at least a natural high-molecular polysaccharide derived from red algae,
By having at least one layer of a mordant and a hydrophilic binder not containing the natural polymer polysaccharide between the dye fixing layer and the layer containing the core natural polymer polysaccharide, coating unevenness is significantly improved, and It is clear that an image without white spot unevenness is obtained.

Similar results were obtained when the support (1) of the dye-fixing element was changed to the support (2).

Similar results were obtained when the support (1) was replaced with the support (2) except for the back layer of the dye-fixing element.

Similar results were obtained when the content of the surface-treated titanium oxide of the support (1) of the dye-fixing element was changed from 10.0 parts to 15.0 parts.

Example 2 A photosensitive element was prepared in exactly the same manner as the photosensitive element of Example 1.

 Next, how to make a dye fixing element will be described.

As shown in the following table, a dye-fixing element (1) was prepared by coating a coating layer having the first to third layers on 100 μm of polyethylene terephthalate to which the first and second back layers had been previously coated.

The thickness of the coating solution from the first layer to the third layer was 12
Coating was carried out by the simultaneous multi-layer coating method as ml / m ² , 35 ml / m ² , and 15 ml / m ² .

After application, a cooling zone of 20 ° C is provided for 10m, 35 ° C, 35% RH
The drying was carried out with a drying air.

Next, a dye-fixing element (5) was prepared in exactly the same manner except that 0.06 g / m ^{2 of} kappa carrageenan was added to the third layer of the dye-fixing element (1).

Further, as shown in the following table, a dye-fixing element (6) was prepared by further adding one layer.

The thickness of the coating solution from the first layer to the fourth layer was 6 m each.
The coating was performed by a simultaneous multilayer coating method at l / m ² , 35 ml / m ² , 6 ml / m ² , and 15 ml / m ² .

After application, a cooling zone of 20 ° C is provided for 10m, 35 ° C, 35% RH
The drying was carried out with a drying air.

The following processing was performed using the above photosensitive element and dye fixing element.

That is, the photosensitive element 101 was exposed to tungsten light at 5000 lux for 1/10 second through a gray filter.

Next, while feeding the exposed photosensitive element at a linear speed of 20 mm / sec, the emulsion surface was supplied with water of 15 ml / m ³ by a wire bar, and immediately thereafter, the dye fixing elements (4) to (6) and the film were fixed. They were overlapped so that the faces touched. The temperature of the absorbed membrane surface is 85
Heating was performed for 15 seconds using a heat roller whose temperature was adjusted to ° C., and peeled off from the dye-fixing element, a clear gray image was obtained on the dye-fixing element.

In the obtained image, density unevenness with a pitch of 5 mm was generated in parallel with the application direction, corresponding to the air volume unevenness of the drying air after application.

The following table shows the results of measuring the density unevenness of the portion where the average density of Y (yellow), M (magenta) and Cy (cyan) in the gray portion is 1.0 by micron densitometry (beam diameter 2 mm).

Further, the number of white spots having a diameter of 3 mm or more generated in the image is shown.

As is clear from the above table, according to the present invention, in the dye-fixing element having a dye-fixing layer containing a mordant and a layer containing at least a natural high-molecular polysaccharide derived from red algae,
By having at least one layer of a mordant and a hydrophilic binder not containing the natural polymer polysaccharide between the dye fixing layer and the layer containing the natural polymer polysaccharide, coating unevenness is significantly improved, and It is clear that an image without white spot unevenness is obtained.

Similar results were obtained even when the thickness of the polyethylene terephthalate of the dye fixing element was changed from 100 μ to 175 μ.

Similar results were obtained when the polyethylene terephthalate of the dye-fixing element was changed to the following support (4) and the back layer was removed.

Continuation of the front page (56) References JP-A-2-235060 (JP, A) JP-A-3-146949 (JP, A) JP-A-1-288854 (JP, A) JP-A-4-3055 (JP) , A)

Claims (2)

(57) [Claims] 1. A dye-fixing element comprising a dye-fixing layer containing a mordant for fixing a mobile dye distributed imagewise on a support and a layer containing at least a natural high molecular polysaccharide derived from red algae. A dye-fixing element comprising at least one layer comprising a mordant and a hydrophilic binder not containing the natural polymer polysaccharide, between the layer and the layer containing the natural polymer polysaccharide. 2. The natural high molecular weight polysaccharide derived from red algae is a natural high molecular weight polysaccharide selected from agar, copper carrageenan, lambda carrageenan, iota carrageenan, and furceleran. Dye fixing element.