JPH04139447A - Dye fixing element - Google Patents

Abstract

PURPOSE:To obviate unequal coating and to prevent the generation of voids and unequal spots by providing at least one layers of layers consisting of a hydrophilic binder which does not contain a mordant and natural high-molecular polysaccharides between a dye fixing layer and a layer contg. the natural high- molecular polysaccharides. CONSTITUTION:The dye fixing layer contg. at least the mordant and the layer contg. the natural high-molecular polysaccharides derived from red algae as well as the intermediate layer between these two layers are provided on the base body to form the above dye fixing element. This intermediate layer is the layer consisting of the natural binder which does not contain the mordant and the natural high-molecular polysaccharides. The intermediate layer contg. the natural high-molecular polysaccharides derived from the red algae and the dye fixing layer are preferably arranged in this order when viewed from the direction where the dyes are successively diffused. The unequal application are greatly improved in this way and the images free from the voids and unequal spots are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an image forming material, and particularly to a dye fixing material that is free from uneven coating and uneven white spots.

(Background Art) Photography using silver halide has been the most widely used method since it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. It is 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,
There is a wet processing type color diffusion transfer method in which an alkali treatment composition is spread in a layer within the laminate or the laminate is immersed in an alkaline treatment liquid.

In addition, in recent years, when photosensitive silver halide and/or organic silver salts are reduced to silver by heat development, diffusible dyes are produced or released in response to or inversely to this reaction, and this diffusive dye is Methods have also been developed in which dyes are transferred by mordants to dye-fixing elements, for example in U.S. Pat. No. 4.46.
No. 3,079, No. 4,474,867, No. 4.
478. No. 927, No. 4.507,380, No. 4,500.626, No. 4,483,914, JP-A No. 58-149046, No. 5B-149047,
No. 59-152440, No. 59-154445, No. 59-165054, No. 59-180548, No. 5
No. 9-168439, No. 59174832, No. 59-
No. 174833, No. 59-174834, No. 59-1
No. 74835, No. 62-65038, No. 61-232
45, European Patent Publication No. 210,660A2, European Patent Publication No. 220
It is described in ゜746A2, etc.

(Problem to be Solved by the Invention) However, in dye fixing elements that fix dyes using mordants in this way, uneven coating of the dye fixing layer is likely to occur due to drying wind, and therefore density unevenness in the output image is likely to occur. There was a problem.

In order to solve the problem of uneven coating, the present inventors used a natural high-molecular polysaccharide derived from red algae, which is known to be prone to gelation. As a result, although it was sufficient to improve coating unevenness, a problem occurred in which white spots frequently appeared.

Here, white spot unevenness refers to a failure in which, when a dye image is transferred to a dye-fixing element, a spot-like area where the dye is not transferred occurs in an area where the dye image should normally be transferred.

Therefore, an object of the present invention is to provide a dye-fixing element that has no uneven coating and no uneven white spots.

(Means for Solving the Problems) The problems of the present invention include a dye fixing layer containing a mordant for fixing a mobile dye imagewise distributed on a support, and a layer containing at least a natural polymeric polysaccharide derived from red algae. The dye fixing element has at least one layer consisting of a mordant and a hydrophilic binder that does not contain the natural polymer polysaccharide between the dye fixing layer and the layer containing the natural polymer polysaccharide. The problem was solved by dye-fixing elements.

The dye fixing element of the present invention is formed by providing on a support at least a dye fixing layer containing a mordant, a layer containing a natural polymeric polysaccharide derived from red algae, and an intermediate layer between the two layers, This intermediate layer is a layer consisting of a hydrophilic binder that does not contain a mordant and the natural polymeric polysaccharide. As the hydrophilic binder used in the intermediate layer, JP-A-62-253
Examples include those described on pages (26) to (28) of No. 159. Specifically, transparent or translucent hydrophilic binders are preferred, and include natural compounds such as proteins or cellulose derivatives such as gelatin and gelatin derivatives, polysaccharides such as starch, gum arabic, dextran, and pullulan, and polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. In addition, super absorbent polymers described in JP-A No. 62-245260, i.e. homopolymers of vinyl monomers having -COOM or -8o3M (M is a hydrogen atom or an alkali metal), these vinyl monomers together, or other vinyl Copolymer with monomer (
For example, sodium methacrylate, ammonium methacrylate, and Sumitomo Chemical (Sumikagel L-5H, a stock company) can also be used. Two or more of these binders may be used in combination.

In the intermediate layer, surfactants, thickeners,
Additives such as matting agents may also be added.

The coating amount of the hydrophilic binder in the intermediate layer can be determined arbitrarily, but it is generally 0.05g per 1rrl' of support.
~10g, particularly about 0.1g~1g is appropriate.

In the present invention, when viewed from the direction in which the dye diffuses,
It is preferable to arrange the dye fixing layer in the intermediate layer between the layers containing the natural polymeric 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.

The relationship between the photosensitive element and the dye fixing element, the relationship with the support,
Regarding the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500.626 can also be applied to the present application.

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

The natural high-molecular polysaccharides derived from red algae used in the present invention include "Food Industry J Vol. 31 (1988) No. 21
Natural polymeric polysaccharides obtained by extraction and purification from red algae listed in Table 1 on page 1 can be mentioned.

Natural high-molecular polysaccharides obtained by extraction and purification from red algae are often a mixture of various types. In the present invention, this mixture can be used as it is, or it can be used alone with even higher purity. Among the natural high-molecular polysaccharides derived from red algae used in the present invention, those particularly suitable for the present invention include agar, kappa carrageenan, lambda carrageenan, iota carrageenan, farcellan, and the like. These substances are also available commercially. For example, kappa carrakinan is available as Tight-gelling agent NK-4 manufactured by Taito Co., Ltd., and lambda carrageenan mixed with a trace amount of kappa-carrageenan is Tight-gelling agent MV manufactured by Taito Co., Ltd.
It is available as . The amount of the natural high-molecular polysaccharide derived from red algae of the present invention can be set arbitrarily, but it is 0.005 to 10 g/rrr per 1 d of support, especially 0.005 to 10 g/rrr, particularly 0.005 to 10 g/rrr per 1 d of support. 01-4
Approximately g/r& is appropriate.

The mordant of the present invention can be arbitrarily selected from commonly used mordants, and among them, polymer mordants are particularly preferred. Here, the polymer mordants include polymers containing tertiary amino groups, polymers containing nitrogen-containing heterocyclic moieties, and polymers containing these quaternary cation groups.

Preferred specific examples of homopolymers and copolymers containing vinyl monomer units having tertiary amino groups include the following. The number in seven units represents mol% (the same applies hereinafter) CH.

112 ”＼.2H8 Such.

Specific examples of homopolymers and copolymers containing vinyl monomer units having tertiary imidazole groups include U.S. Pat. No. 4,282,305, U.S. Pat.
No. 3,148,061, JP 60-118834
No. 60-122941, JP-A-62-24404
3. The following may be mentioned, including the mordant described in JP-A No. 62-244036.

-CH2-CH size 100T -fCH.

CH-)7-1116CH.

CH+rT- 1CH2 -CHsr--Ichiichiko CH2 -CH child CH3 fCH2 CHsuh ``-6CH2C Puni- H3 CH3 - at CH2 CHsu[-1CH2Csu- CH2 in one CH-Kunchoichigo CH2CH-Me - at CH2 CH Shit-111 (2CHi-Ding) Such.

Preferred specific examples of homopolymers and copolymers containing vinyl monomer units having quaternary imidazolium salts include British Patent No. 2,056,101, British Patent No. 2.093,
No. 041, same No. 1. No. 594°961, U.S. Patent No. 4
, No. 124.386, No. 4.115,124, No. 4. 273. The following may be mentioned, including the mordants described in No. 853, No. 4,450,224, and JP-A-48-28325.

-(CH3-CHtiTO CH.

-fCH.

-CH dimension CHt-CH, -0H - for CH.

-CH-Si-ICH2 -CH dimension] C.O.

CH.

CH CH.

(Cut C size π1CHZ CHsriCHICH
Sweet H2 C0se C) 12 CH-CH20H CH etc.

Other preferred specific examples of homopolymers and copolymers containing vinyl monomer units having a quaternary ammonium salt include U.S. Pat.
No. 98,088, No. 3゜958.995, Japanese Unexamined Patent Publication No. 6
No. 0-57836, No. 60-60643, No. 60-1
No. 22940, No. 60-122942, No. 6.0-2
The following may be mentioned, including the mordant described in No. 35134.

CH3 廿CH, -9H-half π Such.

CH.

Others, U.S. Patent No. 2,548,564, U.S. Patent No. 2.4
No. 84,430, same No. 3. 148. Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in U.S. Pat. No. 3,756,814, etc.; U.S. Pat.
859.096, British Patent No. 4,128,538, British Patent No. 1,277.453, etc.; polymer mordant side capable of crosslinking with ceratin, etc.; U.S. Patent No. 3.958.995; , No. 2,721.852, No. 2
, 798,063, and the specifications of JP-A-54-115228, JP-A-54-145529, JP-A-54-26027, etc.; U.S. Patent No. 3. ．．
Water-insoluble mordant disclosed in US Pat. No. 898,088: U.S. Pat.
No. 37333), a reactive mordant capable of forming a covalent bond with the dye disclosed in the specification, etc., and also US Pat. No. 3,70
9゜690, same No. 3,788,855, same No. 3゜6
No. 42.482, No. 3,488,706, No. 3,
No. 557,066, same No. 3. 271. No. 147, No. 3,271,148, JP-A No. 5071332, No. 53-30328, No. 52-155528, No. 53
Examples include mordants disclosed in Japanese Patent No. 125 and No. 53-1024.

Others, U.S. Patent No. 2,675,316, U.S. Patent No. 2,8
Mention may also be made of the mordants described in US Pat. No. 82,156.

The molecular weight of the polymer mordant of the present invention is 1. 000~1,
000,000 is appropriate, especially 10°000 to 20
0,000 is preferred.

The photosensitive element of the present invention basically has a photosensitive silver halide, a binder, and a dye-providing compound on a support, and can further contain other additives as required. These components are often added to the same layer, but if they are in a reactable state, they can be divided and added to separate layers. For example, when a colored dye-providing compound is present in the lower layer of the silver halide emulsion, it prevents a decrease in sensitivity. In the case of a thermal development method, the reducing agent or its precursor is preferably incorporated into the photosensitive element, but it may also be supplied from the outside, for example, by diffusing it from a dye fixing element, which will be described later.

The amount of the reducing agent or its precursor used is 0.001 to 20 mol, particularly 0.01 to 1 mol, per mol of silver halide.
0 mol is preferred.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, macenta, and cyan, at least three silver halide emulsion layers each sensitive to a different spectral region are used in combination.

For example, there are combinations of three layers such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can be arranged in a variety of arrangements known from conventional color photosensitive elements.

Further, each of these photosensitive layers may be divided into two or more layers as necessary. For example, each photosensitive layer may have two layers, a high-sensitivity layer and a low-sensitivity layer, or three layers, a high-sensitivity layer, a center layer, and a low-sensitivity layer.

The photosensitive element can be provided with various auxiliary layers such as a protective layer, a subbing layer, an intermediate layer, a yellow filter layer, an anti-halley/con layer, and a backing layer.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Any of silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used.

The silver halide emulsion used in the present invention may be a surface latent image type emulsion 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 and a photofog. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases.

The silver halide emulsion may be monodisperse or polydisperse, or a mixture of monodisperse emulsions may be used.

Particle size is 0.1-2 μm, especially 0.2-1.5 μm
is preferred. The crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular with a high aspect ratio, or any other form.

Specifically, U.S. Patent No. 4,500.626, column 50;
No. 4.628.021, Research Disclosure (hereinafter abbreviated as RD) 17029 (1978
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive elements, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. 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 photosensitive silver halide used in the present invention is in the range of 1 to 1 Og/ni' in terms of silver.

The silver halide used in the present invention may be spectrally sensitized with methine dyes or others. Dyes that may be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, U.S. Pat.
17029 (1978), pages 12-13, and the like.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, the emulsion may contain a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in U.S. Pat. .615゜641, patent application 1986-22
6294 etc.).

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
It may be carried out before or after nucleation of silver halide grains according to No. 756 and No. 4,225,666. The amount added is generally about 10-1 to lo-2 mol per mol of silver halide.

In the heat development method, an organic metal salt can be used together with the photosensitive silver halide as an oxidizing agent. Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agents include U.S. Pat.
There are benzotriazoles, fatty acids, and other compounds described in column 53, etc. 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 as described in JP-A-61-249044. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50 to 10 g/r in terms of silver.
rf is suitable.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD176
43 (1978) pages 24-25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and phosphoric acids described in JP-A-59-111636. Metal salts thereof, acetylene compounds described in JP-A No. 62-87957, and the like can be used.

Examples of dye-providing compounds that can be used in the present invention include compounds (couplers) that form dyes through oxidative coupling reactions. This coupler is 4
It may be an equivalent coupler or a 2-equivalent coupler. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction. Specific examples of developers and couplers can be found in “The Theory of the Photographic Process” by James James, 4th edition (T.
, H. James"The Theory of t
hePhotographic Process”)
pp. 291-334 and 354-361, Japanese Patent Application Publication No. 1975.
No. 8-123533, No. 58-149046, No. 58
-149047, 59-111148, 59-
No. 124399, No. 59-174835, No. 5923
No. 1539, No. 59-231540, No. 60-295
No. 0, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-66249, Special Publication No. 5
It is described in detail in No. 2-24849, JP-A-53-129036, etc.

Further, as another example of the dye-providing compound, there can be mentioned a compound having a function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula [:LI).

(Dye-Y), -Z (L I]Dye
represents a dye group, -temporally shortened dye group or dye precursor group, Y represents a mere bond or linking group,
Z corresponds to or inversely corresponds to a photosensitive silver salt having a latent image (Dye-Y). A method that causes a difference in the diffusivity of the compound represented by -Z, or emits Dye and causes a difference in diffusivity between the released Dye, (Dye-Y), and -Z. represents a group having the properties, n is 1
or 2, and when n is 2, the two Dye-Ys may be the same or different.

Specific examples of the dye-providing compound represented by the general formula [LI] include the following compounds (1) to (2).

Note that ■ to ■ below are those that form a diffusive dye image (positive dye image) in reverse response to silver halide development.
(2) and (2) form a diffusive dye image (negative dye image) in response to silver halide development.

■US Patent No. 3: 134.764, US Patent No. 3゜36
2.819, 3,597.200, 3,5
No. 44,545, same No. 3. 482. A dye developer in which a hydroquinone developer and a dye component are linked together, as described in No. 972, can be used.

This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

■As described in US Pat. No. 4,503,137, etc., non-diffusible compounds that release diffusible dyes in an alkaline environment but lose this ability when reacted with silver halide can also be used. Examples include U.S. Patent No. 3,980
Compounds that release diffusible dyes through intramolecular nucleophilic substitution reactions, such as those described in U.S. Patent No. 4,199,3
Examples include compounds that release a diffusible dye through an intramolecular rewinding reaction of an isoxacilone ring, as described in No. 54 and the like.

■US Patent No. 4,559,290, European Patent No. 220
．． As described in No. 746A2, Kokka Shishishi 87-6199, etc., non-diffusible compounds that react with the reducing agent remaining unoxidized by development to release a diffusible dye can also be used.

Examples include U.S. Patent No. 4. 139. No. 389, No. 4,139,379, JP-A-59185333
Compounds that release diffusible dyes by intramolecular nucleophilic substitution reaction after being reduced, as described in US Pat. , No. 61-88257, RD2
4025 (1984), etc., a compound that releases a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3.008,588A, JP-A-1986-
No. 142530, U.S. Pat. No. 4,343.893, U.S. Pat. No. 4,619,884, and other compounds that release a diffusible dye by cleaving a single bond after reduction; U.S. Pat. No. 4,450 Nitro compounds that release diffusible dyes after accepting electrons, as described in U.S. Patent No. 223, etc.;
, 609.610, etc., which release a diffusible dye after electron acceptance.

Also, more preferably, European Patent No. 220.7
No. 46A2, Publication Edaburi 87-6199, Patent Application 1986-3
Compounds having an N-X bond (X represents oxygen, sulfur, or nitrogen atom) and an electron-withdrawing group in one molecule, as described in No. 4953, No. 62-34954, etc., patent application No. 62-106
A compound having 5O2-X (X has the same meaning as above) and an electron-withdrawing group in one molecule described in No. 885, patent application No. 1988-
106895, a po-x bond (X
is the same meaning as above) and an electron-withdrawing group, and a compound having a C-X' bond (X' is the same as X or represents -5O2-) in one molecule as described in Japanese Patent Application No. 106887/1987. Examples include compounds having an electron-withdrawing group.

Among these, compounds having an N-X bond and an electron-withdrawing group in the -molecule are particularly preferred. A specific example is European Patent No. 22
Compounds (1) to (3) described in No. 0,746A2,
(7)-(10), (mouth, (13), (15), (2
3) - (26), (31), (32), (35), (3
6), (40), (41), (44), (53) to (5
9), (64), (70), and the compounds (11) to (23) of Publication Shishishi 87-6199.

■A compound that is a coupler that has a diffusible dye as a leaving group and releases the diffusible dye upon reaction with the oxidized form of a reducing agent (D
DR coupler) can be used. Specifically, British Patent No. 1.3.30,524, Japanese Patent Publication No. 48-39165,
U.S. Patent No. 3,443°940, U.S. Patent No. 4,474,8
There are those described in No. 67, No. 4゜483.914, etc.

■Reducing to silver halide or organic silver salt,
Compounds that release diffusible dyes upon reduction of their partner (DRR)
compounds) can be used. Since this compound does not require the use of any other reducing agent, it is preferable since there is no problem of image staining due to oxidative decomposition products of the reducing agent. Representative examples include U.S. Patent No. 3,928°312, U.S. Patent No. 4.053,312,
4゜055.428, 4,336,322, JP-A-59-65839, JP-A-59-69839,
No. 53-3819, No. 51-104343, RD1
7465, U.S. Patent No. 3,725°062, U.S. Patent No. 3
, No. 728,113, No. 3443.939, JP-A No. 513-116537, No. 57-179840,
It is described in US Pat. No. 4,500°626 and others.

Specific examples of DRR compounds include those described in the aforementioned U.S. Patent No. 4.
500. The compounds described in columns 22 to 44 of No. 626 can be mentioned, and among them, compounds (1) to (3), 00) to (13), and (16) described in the above-mentioned US patent can be mentioned.
)~(]9), (28)~(30), (33)~(35
), (38) to (40), and (42) to (64) are preferred.

Also useful are the compounds described in U.S. Pat. No. 4,639,408, columns 37-39.

In addition, as dye-donating compounds other than the couplers and general formula [LI] mentioned above, dye silver compounds in which an organic silver salt and a dye are combined (Research Disclosure Magazine 1978
May issue, pp. 54-58), azo dyes used in heat-developable silver dye bleaching methods (U.S. Pat. No. 4,235,957,
Research Disclosure magazine, April 1976 issue,
30-32), leuco dyes (U.S. Pat. No. 3.98)
5. No. 565, No. 4,022,617, etc.) can also be used.

The above-mentioned hydrophobic additives such as dye-donating compounds and diffusion-resistant reducing agents are described in US Pat. 322. They can be incorporated into the layers of the light-sensitive element or dye-fixing element by known methods such as the method described in No. 027. In this case, Japanese Unexamined Patent Publications No. 59-83154, No. 59-178451, No. 5
No. 9-178452, No. 59-178453, No. 59
-178454, 59-178455, 59-
A high boiling point organic solvent such as that described in No. 178457, etc.
If necessary, it can be used in combination with a low boiling point organic solvent having a boiling point of 50°C to 160°C.

The amount of high-boiling organic solvent is 1 g of the dye-donating compound used.
10 g or less, preferably 5 g or less. Also, ice per 1g of binder, or even 0.5
cc or less, particularly 0.3 cc or less is suitable.

Dispersion methods using polymers described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used.

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

Various surfactants can be used when dispersing hydrophobic compounds in hydrophilic colloids. For example, JP-A-59
-157636, pages (37) to (38), those listed as surfactants can be used.

In the present invention, a compound that activates development and simultaneously stabilizes images can be used in the photosensitive element. For specific compounds preferably used, see U.S. Patent No. 4,50.
It is described in columns 51-52 of No. 0.626.

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

Further, a dye-donating compound having reducing properties, which will be described later, is also included (in this case, other reducing agents can also be used in combination). Further, a reducing agent precursor that does not itself have reducing properties but exhibits reducing properties by the action of a nucleophile or heat during the development process can also be used.

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

More specifically, U.S. Patent No. 4. 500. Columns 49-50 of No. 626, No. 30 of No. 4,483,914
~Column 31, No. 4,330,617, No. 4,590
, No. 152, JP-A-60-140335 No. (17)
~(18) pages, No. 57-40245, No. 56-138
No. 736, No. 59-178458, No. 59-5383
No. 1, No. 59-182449, No. 59-182450
No. 60-119555, No. 60-128436 to No. 60-128439, No. 60-19854
No. 0, No. 60-181742, No. 61-259253
No. 62-244044, No. 62-131253 to No. 62-131256, European Patent No. 220,
There are reducing agents and reducing agent precursors described in pages 78 to 96 of No. 746A2.

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

If a diffusion-resistant reducing agent is used, an electron transfer agent and/or electron transfer agent is optionally added to facilitate electron transfer between the diffusion-resistant reducing agent and the developable silver halide. Combinations of precursors can be used.

The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is greater 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 one of the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive element, and preferably hydroquinones, Examples include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A-53-110827, and dye-donating compounds with diffusion resistance and reducing properties described below.

Examples of dye-donating compounds with reducing properties include the dye developing agents mentioned below, and those disclosed in U.S. Pat. There are the compounds described above, DRR compounds, etc.

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

Color mixing inhibitors include hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers,
Examples include sulfonamide phenol derivatives.

As filter dyes or irradiation or antihalation dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, azo dyes are preferably used, in addition to which cyanine dyes, azomethine dyes, triarylmethane dyes are used. Dyes, phthalocyanine dyes, are also useful.

Examples of development inhibitors, antifoggants, and photographic stabilizers include azoles such as benzothiazolium salts, nitroimidazoles, nitsobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, and mercaptobenzothiazoles. mercaptobenzimidazole, mercaptothiadiazole, aminotriazole, benzotriazole, nitrobenzotriazole, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidine; mercaptotriazine; e.g. oxadrine Thioketo compounds such as thiones;
Azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy substituted (1,3,3a
, 7) Tetraazaindenes), pentaazaindenes, etc.: Examples include benzenesulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and the like.

As an optical brightener, Veenkataraman
Edited by “The Chemistry of 5ynth”
ic Dyes” Volume V, Chapter 8 can be used.

More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds,
Examples include naphthalimide compounds, pyrazoline compounds, carbostyril compounds, and the like.

Antifading agents other than antioxidants include (bissalicylaldoximide) nickel complex and (bis-N, N
- dialkyldithiocarbamad) nickel complexes (U.S. Pat. No. 4,241,155, U.S. Pat. No. 4,245,018, columns 3 to 36, U.S. Pat. No. 4,254.
No. 195, columns 3 to 8, JP-A-50-87649, 6
No. 2-174741, No. 6I-88256 (27) ~
(29) page, Japanese Patent Application No. 61-234103, No. 62-3
Compounds described in No. 1096 etc. and Bensito 1.1
Azol compounds (U.S. Pat. No. 3,533.794, etc.), 4-thiazolidone compounds (U.S. Pat. No. 3,35, etc.)
No. 2,681, etc.) benzophenone compounds (Japanese Unexamined Patent Publication No. 4
There are other ultraviolet absorbers described in JP-A-54-48535, JP-A-62-136641, JP-A-61-88256, JP-A-62260152, etc.

The development stopper may be a compound that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development immediately after proper development, or a compound that inhibits development by interacting with silver and silver salts. be.

This is often used in thermal development methods, specifically acid precursors that release acids when heated, electrophilic compounds that undergo a substitution reaction with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their like. Precursors and the like can be mentioned.

For more details, see JP-A No. 62-253159 (31) - (
It is described on page 32).

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

An example of this is No. 26 of JP-A No. 62-253159.
) to pages (28). Specifically, there are those listed as binders for the intermediate layer of the dye fixing element.

When employing a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned super absorbent polymer allows rapid absorption of water. Furthermore, when a highly water-absorbing polymer is used in the dye-fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye-fixing element to another object after transfer.

In the present invention, the amount of binder applied is 2 per lrd.
The amount is preferably 0 g or less, particularly 10 g or less, and more preferably 7 g or less.

Hardeners used in the constituent layers of light-sensitive elements and dye-fixing elements include U.S. Pat.
Examples include hardeners described in No. 1-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene bis(
(vinylsulfonylacetamide) ethane, etc.) N-methylol hardeners (dimethylol urea, etc.) or polymer hardeners (compounds described in JP-A-62-234157, etc.).

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

Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive element layers. It has functions such as promoting the movement of dye from the dye fixation layer to the dye fixed layer, and from a physicochemical function, it has a function such as base or base precursor nucleophilic compound, high boiling point organic solvent (oil),
It is classified into thermal solvents, surfactants, and compounds that interact with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Details of these can be found in U.S. Pat. No. 4,678,739, columns 38-40.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Beckmann rearrangement. Specific examples include U.S. Patent No. 4,511.493;
It is described in Japanese Patent Application Laid-Open No. 62-65038.

In a system in which thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a base precursor in the dye fixing element in order to improve the storage stability of the photosensitive element.

In addition to the above, combinations of poorly soluble metal compounds and compounds capable of complexing reaction with metal ions constituting this poorly soluble metal compound (referred to as complex-forming compounds), as described in European Patent Publication No. 210,660, and special Kaisho 61-232451
Compounds that generate bases by electrolysis, such as those described in this issue, can also be used as base precursors.

The former method is particularly effective. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive element and the dye-fixing element separately.

Various surfactants can be used in the constituent layers of the photosensitive element and the dye fixing element for the purposes of coating aids, improving peelability, improving slipperiness, preventing static electricity, accelerating development, and the like. Specific examples of surfactants are given in JP-A-62-173463 and JP-A-62-18.
It is described in No. 3457, etc.

The constituent layers of the photosensitive element and dye fixing element are coated with improved slipperiness,
An organic fluoro compound may be included for the purpose of preventing static electricity and improving peelability. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
20944, 62-135826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the photosensitive element and the dye fixing element. As a matting agent, silicon dioxide, polyolefin or polymethacrylate may be used.
In addition to the compounds described in No. 6, page (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc.
There is a compound described in No. 10065.

In addition, the constituent layers of the photosensitive element and the dye fixing element may contain a thermal solvent, an antifoaming agent, an antibacterial agent, colloidal silica, and the like. Specific examples of these additives are given in JP-A-61-
No. 88256, pages (26) to (32).

As the support for the photosensitive element and the dye fixing element, those that can withstand processing temperatures are used.

-For boat fishing, paper and synthetic polymers (films) can be used. Specifically, films made from polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (e.g. triacetyl cellulose), films containing pigments such as titanium oxide, and polypropylene, etc. Film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coachite paper (particularly cast coated paper), metal, cloth, glass, etc. are used.

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

In addition, Japanese Patent Application Laid-Open No. 62-25315953159 (
The supports described on page 31) can be used.

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

Methods of exposing and recording images on a photosensitive element include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or negative film using a printer or enlarger, and using a copying machine. A method in which the original image is scanned and exposed through a slit using an exposure device, etc. A method in which image information is transmitted via an electric signal to a light emitting diode, various lasers, etc. for exposure; There are methods of outputting the image to an image display device such as a spray display or a plasma display, and exposing the light directly or through an optical system.

Light sources for recording images on the photosensitive element include natural light, tank lamps, light emitting diodes, laser light sources, CRT light sources, etc., as mentioned above, such as U.S. Pat. No. 4,500,6.
The light source described in No. 26, column 56 can be used.

The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), and images obtained by dividing an original image into a large number of pixels using a scanner. signal, CG, C
Image signals created using a computer such as AD 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, when using a so-called two-sheet type photographic element in which a photosensitive layer and a dye fixing layer are formed on separate supports, typical steps include (i) exposure process - thermal development process - photosensitive element and dye fixing element; - Transfer process - Peeling process (ii) Exposure process - Lamination process of photosensitive element and dye fixing element - Heat development/transfer process - Peeling process (iii) Exposure process - Heat development process - Solvent application process - Superposition process of photosensitive element and dye fixing element - Transfer process - Peeling process (iv) Exposure process - Solvent application process - Superposition process of photosensitive element and dye fixing element - Heat development/transfer process Peeling process to be listed. I can do it. The peeling step may be omitted depending on the configuration of the dye fixing element.

The above process is a convenient classification, and there are cases where multiple steps are performed consecutively, such as when heat development is performed in tandem with exposure, or when one process is performed in multiple stages, and there are cases where there is a gap between the steps. Including cases that are not clearly classified. The combination of processes to be selected depends on the base generation method, for example, incorporating a thermally decomposable base precursor or generating a base by reacting compounds contained in two photographic elements in the presence of a solvent. It can be selected, and it can also be selected by the use of accelerators to control the speed of development transfer.

The heating temperature in the heat development step can be developed at about 506C to about 250C, and particularly useful is about 506C to about 180C. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed. In the latter case, the heating temperature in the transfer step can be in the range from the temperature in the heat development step to room temperature, but it is particularly preferable to set the heating temperature to 50° C. or higher and about 10° C. lower than the temperature in the heat development step. .

Dye migration can also be caused by heat alone, but a solvent may be used to promote dye migration.

Also, JP-A-59-218443, JP-A No. 6123805
6, etc., a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method, the heating temperature is 50
The temperature is preferably 50°C or higher and 100°C or lower when the solvent is water.

Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixing layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may Those described in the section on formation accelerators can be used. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a complex-forming compound with a sparingly soluble metal salt, etc. may be included in the solvent.

These solvents can be used in a method in which they are applied to a dye-fixing element, a photosensitive element, or both.

The amount used may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating).

Examples of methods for applying a solvent to the photosensitive layer or dye fixing layer include the method described in JP-A-61-147244 (No. 26). It can also be incorporated into the element, the dye-fixing element, or both.

Further, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated into the photosensitive element or dye fixing element. The hydrophilic thermal solvent may be incorporated into either the photosensitive element or the dye fixing element, or may be incorporated into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto.

Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alnyls, oximes, and other heterocycles.

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

Heating methods in the development and/or transfer process include contact with a heated block or plate, contact with a hot plate, hot presser, heat roller-halogen lamp heater, infrared and far-infrared lamp heater, etc. For example, it may be passed through a high-temperature atmosphere. Alternatively, a resistive heating layer may be provided on the photosensitive element or the dye fixing element, and the layer may be heated by supplying electricity to the layer.

As the heat generating layer, those described in JP-A-61-145544 and the like can be used.

The pressure conditions and method of applying pressure when overlapping the photosensitive element and the dye fixing element and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 1472-1986.
No. 44 (The method described in No. 27 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A No. 5975247, No. 59-177547, No. 59181353, No. 60
Apparatuses described in Japanese Utility Model Application Publication No. 18951, Japanese Utility Model Application Publication No. 61-25944, etc. are preferably used.

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

This wet color diffusion transfer method is described, for example, in Belgian Patent No. 757,959. The dye-providing compounds that can be used in this wet color diffusion transfer method include the above-mentioned -
Examples include compounds of the form [L■].

The photographic elements used in this color diffusion transfer process will be described in more detail below.

The photographic element in this case is preferably a film unit that is a combination of a light-sensitive element and a dye-fixing element.

In a typical form of a film unit, the above-mentioned dye fixing element and photosensitive element are laminated on one transparent support, and after the transferred 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,
In a preferred embodiment of the light-sensitive element, a blue-sensitive emulsion layer,
A combination of a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a combination of a green-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer. A yellow dye-providing compound, a magenta dye-providing compound, and a cyan dye-providing compound are combined in each of the above-mentioned emulsion layers. 700
(This refers to an emulsion layer that is sensitive to light with a wavelength of 740 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 process can be completed in a bright place. Further, if desired, a peeling layer may be provided at an appropriate position so that all or part of the photosensitive element can be peeled off from the dye-fixing element (such an embodiment is described in, for example, Japanese Patent Laid-Open No. 56-678).
40 and Canadian Patent No. 674,082).

In another form that does not require peeling, the photosensitive element described above is coated on one transparent support, a white reflective layer is coated thereon, and a dye fixing element is further laminated thereon. Regarding an embodiment in which a dye fixing element, a white reflective layer, a peeling layer, and a photosensitive element are laminated on the same support, and the photosensitive element is intentionally peeled off from the dye fixing element, US Pat. 73
0. It is described in No. 718. On the other hand, there are two typical forms in which a photosensitive element and a dye fixing element are separately coated on two supports, one of which is a peelable type and the other a peelable type. To explain these in detail, a preferred embodiment of the peelable film unit has a light reflecting layer on the back surface of the support and at least one dye fixing layer coated on the surface thereof. In addition, the photosensitive element is coated on a support having a light-shielding layer, and the surface coated with the photosensitive layer and the mordant layer do not face each other before exposure is completed, but after the completion of exposure (for example, during development), the surface coated with the photosensitive layer is It is devised so that it can be turned upside down and overlapped with the surface on which the dye fixing layer is applied. Immediately after the transfer image is completed with the mordant layer, the photosensitive element is peeled off from the dye fixing element.

Further, in a preferred form of the peel-free film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-blocking layer, The surface coated with the photosensitive layer and the surface coated with the mordant layer are stacked facing each other.

The wet color diffusion transfer photographic element described above may further be combined with a pressure-rupturable container (processing element) containing an alkaline processing liquid. In particular, in a peel-free type film unit in which a dye-fixing element and a photosensitive element are laminated on one support, it is preferable that the processing element is disposed between the photosensitive element and a cover sheet overlaid thereon.

Further, in the case where the photosensitive element and the dye fixing element are separately coated on two supports, it is preferable that the processing element is placed between the photosensitive element and the dye fixing element at the latest during the development process. Depending on the form of the film unit, the processing element preferably contains a light shielding agent (carbon black, pH-dependent dye, etc.) and/or a white pigment (titanium oxide). In addition, in wet color diffusion transfer film units, a neutralization timing function consisting of a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, in the dye fixing element, or in the photosensitive element. preferable.

Specific examples will be described below, but the present invention is not limited to these examples.

[Example 1] This section describes how to make photosensitive elements.

Photosensitive silver halide emulsion (for red-sensitive emulsion layer) A well-stirred gelatin aqueous solution (20g of gelatin in 800ml of water,
0.3 g of potassium bromide, 6 g of sodium chloride, and 3.0 ■ of the following chemical A were added and kept at 50°C), and the following solutions (1) and (If) were added at the same time at equal flow rates over 30 minutes. did. After that, the following solution (III) and (IV
) was added at the same time over a period of 30 minutes. Also (III)
, A solution of the following dye mixture was added 3 minutes after the start of addition of the solution (IV).

After washing with water, desalting, lime treatment, adding 22 g of ossein seratin to adjust the pH to 6.2 and pAg to 7.7, and then adding sodium thiosulfate and 4-hydroxy-6-methyl-1,3
,3a,7-chitrazaindene, adding chloroauric acid to 60
Optimally chemically sensitized at ℃. In this way, a monodisperse cubic silver chlorobromide emulsion with an average grain size of 0.38 μm was obtained. Yield was 635g.

Sensitizing dye Sensitizing dye photosensitive layer Silver halide emulsion (for green photosensitive layer) A well-stirred aqueous solution (20 g of ceratin, 0.30 g of potassium bromide, 6 g of sodium chloride, and 0.01 g of chemical A in 730 g of water)
Add 5g and keep warm at 60°0℃) to the following (1)
The solution and solution (II) were added simultaneously over 30 minutes. Next, solution (III) and solution (rV) were added over 30 minutes, and 1 minute after the addition was completed, a solution of the following sensitizing dye was added.

After washing with water and desalting, add 20g of seratin and adjust the pH. Triethylthiourea, chloroauric acid, 4-hydroxy-6-
Optimal chemical sensitization was performed using methyl-1,3,3a,7-titrazaindeso.

The resulting emulsion was a monodisperse cubic emulsion with an average grain size of 0.4 microns and a finished weight of 630 g.

Sensitizing dye photosensitive silver halide emulsion (photosensitive layer) A well-stirred aqueous solution of ceratin (20 g of ceratin, 3 g of potassium bromide, and 0.03 g of the following chemical A in 800 d of water)
and HO(CH2>l S (CHri2 S (CH2)2
(0.25 g of 0H was added and kept at 50°C), and the following solutions (1) and (If) were added simultaneously over 30 minutes. Thereafter, the following solutions (III) and (IV) were simultaneously added over 20 minutes. Further, after the addition of the solution (III) was completed, a solution of the following sensitizing dye was added for 5 minutes.

After washing with water and desalting, 20 g of lime-treated ossein seratin was added to adjust the pH to 6.2 and pAg to 8.5, and then sodium thiosulfate and 4-hydroxy6-methyl-1,3,3
Optimal chemical sensitization was carried out by adding a, 7-chitrazaindene and chloroauric acid. Thus the average particle size, 0.40
600 g of a monodisperse dodecahedral silver iodobromide emulsion of μ was obtained.

Sensitizing Dye A method for preparing a dispersion of sensitizing dye (1, Ji,) tbtJht'i, Nh1r zinc hydroxide will be described.

12.5 g of zinc hydroxide with an average particle size of 0.2μ, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate in 100 ml of a 4% aqueous solution of Seratin.
added to. This was ground in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm, and then the glass beads were separated to obtain a dispersion of zinc hydroxide.

A method for preparing an activated carbon dispersion will be described.

Wako Tsumugi Pharmaceutical Industry (Activated carbon powder (reagent, special grade) made by Kiki) 2.
5g, Kao soap (Kikusei Demol N1g1 polyethylene glycol nonylphenyl ether 0.25 as a dispersant)
g was added to 100 ml of 5% aqueous seratin solution, and 120 m
Pulverized for minutes. Separate the glass beads and reduce the average particle size to 0.5
A dispersion of μ activated carbon was obtained.

A method for preparing a dispersion of an electron transfer agent will be described.

Add 10 g of the electron transfer agent [phase] below, 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5 g of the anionic surfactant below to a 5% aqueous seratin solution, and mill to obtain an average particle size of 0.75 mm. Grind for 60 minutes using glass beads.

The glass beads were separated and the average particle size was 0. A 4μ electron transfer agent dispersion was obtained.

Electron transfer agent [Phase] Anionic surfactant CH, C00CH, CH(C2H5)C4H9N a
Oh S -CHCooCl(,C)l(C2H5)C
A method for preparing a seratin dispersion of a 4H1 dye-providing compound will be described.

Yellow, magenta, and cyan were each weighed according to the prescriptions in the table below, 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-treated gelatin, 0.6 g of sodium dodecylhensensulfonate, and 5 Orrl of water? After stirring and mixing, the mixture was dispersed using a homogenizer at 110,000 rpm for 10 minutes.

These dispersions are called gelatin dispersions of yellow, magenta, and cyan dye-providing compounds, respectively.

Next, we will discuss how to make a gelatin dispersion of electron donor (2) for the intermediate layer.

The following electron donor ■23.6g and the above high boiling point solvent ■8
．． 5g to 30mI of ethyl acetate! In addition, the mixture was heated and dissolved at 60°C to form a homogeneous solution. This solution, 100 g of a 10% aqueous solution of lime-treated gelatin, and 0.25 g of sodium bisulfite.
g, 0.3 g of sodium dodecylbenzenesulfonate, and 30 ml of water were stirred and mixed with a homogenizer for 10 g.
Dispersion was carried out at 10,000 rpm for 1 minute. This dispersion is called a dispersion of seratin with electron donor (2).

Dye-donating compound (1) Yellow dye-providing compound CONHC16H31(n) (2) Magenta dye-providing compound (3) Cyan dye-providing compound Electron donor■ High boiling point solvent■ Electron transfer agent precursor■ H table 1゜ Configuration of photosensitive element 101 (Note 1) Surfactant ■ (Note 2) Surfactant ■ (Note 3) Water-soluble polymer SO,K (Note 4) Antifoggant ■ (Note 5) Surfactant ■ (Note 6) Surfactant ■ (Note 7) Hardener ■ 2-bis(vinylsulfonylaceto) amido)ethane (Note 8) Antifoggant @ Next, we will discuss how to make the dye fixing element.

As shown in the following table, a dye fixing element (1) was prepared by coating a coating layer consisting of the first to third layers on a support (1) on which the first and second hack layers were coated in advance. Ta.

In addition, the coating liquid film thickness from the first layer to the third layer was 12
Coating was carried out using a simultaneous multilayer coating method at a rate of 1 nl/rrr, 35 J/rf, and 15 m//rrl'.

After application, a cooling zone of 20°C was provided, and the temperature was increased to 35°C.
Drying was performed using dry air at 135% RH.

Composition of dye fixing element (1) Configuration of support fl) Silicone oil (1) H3 H3 H3 Surfactant (1) Surfactant (2) C, F, □5O2NCH2C○OK C,H.

Surfactant (3) CH3 H2, C0NHCH2CH, CH2NCH2COOH3 CH2COOCH, CHC, H.

N　a　03 CHCOOCH2CHC,H9 2H5 Fluorescent brightener (1) 2゜ Screw Turnya Butylbenzo Oxacylyl (2)) Thiophene Surfactant (5) C3H.

C,F,,S○,N (CH2C840)4SO,Na Water-soluble polymer Sumikagel L-5-H (manufactured by Sumitomo Chemical ■) Water-soluble polymer dextran (molecular weight 70,000) Mordant SO2 and high boiling point solvent (1) Chloride Paraffin (manufactured by Ajinomoto, Empara 40) Maddening agent (1 "benzoguanamine resin (average particle size 15μ) reducing agent fl) Next, except for adding 0.06 g/l +? of copper carrageenan to the third layer of the dye fixing element (1) In exactly the same way,
A dye fixing element (2) was created.

Furthermore, as shown in the table below, one layer is added to the dye fixing element (3
)It was created.

In addition, the coating liquid film thickness from the first layer to the fourth layer was set to 6.
ml/rn', 35i/rr? , 6-/d, 15
Coating was performed using a simultaneous multilayer coating method at J/m'.

After coating, a 10 m cooling zone at 20°C was established and the temperature was increased to 35°C1.
Drying was performed using dry air at 35% RH.

The following processing was carried out using the photosensitive element and dye fixing element having the structure of dye fixing element (3).

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

Next, while feeding this exposed photosensitive element at a linear speed of 20 mm/sec, 15 d/ni' of water was supplied to the emulsion surface using a wire bar, and immediately after that, dye fixing elements (1) to (3)
) and the membrane surfaces were placed in contact with each other. When heated for 15 seconds using a heat roller whose temperature was adjusted to 85°C, which is the temperature of the film surface that absorbed water, and peeled it off from the dye fixing element,
A sharp gray image was obtained on the dye fixing element.

The obtained image shows that, in response to the unevenness of the drying air volume after application,
Density unevenness of 5 pitches occurred parallel to the coating direction.

The average density of each of Y (yellow), M (macenta), and Cy (cyan) in the gray part is 1. The results of measuring the density unevenness in the 0 portion by microdensitometry (beam diameter 2 mm) are shown in the following table.

Furthermore, the number of white spots with a diameter of 3 mm or more occurring in the image is shown.

As is clear from the above table, according to the present invention, in a dye fixing element having a dye fixing layer containing a mordant and a layer containing at least a natural polymer polysaccharide derived from red algae, the dye fixing layer and the natural polymer polysaccharide By growing at least one layer consisting of a hydrophilic binder that does not contain a mordant and the natural polymeric polysaccharide between the layer containing the natural polymeric polysaccharide, coating unevenness is significantly improved and an image without uneven white spots can be obtained. It is clear that

Note that similar results were obtained even when the support (1) of the dye fixing element was replaced with the support (2).

In addition, excluding the back layer of the dye fixing element, the support (1)
Similar results were obtained even when the substrate was changed to support (2).

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

Structure of Support (2) Structure of Support (3) Example 2 A photosensitive element was prepared in exactly the same manner as the photosensitive element of Example 1.

Next, we will discuss how to make the dye fixing element.

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

In addition, the coating liquid film thickness from the first layer to the third layer was 12
d/fff', 35J/rrf', and 15m//m', and were coated using a simultaneous multilayer coating method.

After coating, a 10 m cooling zone at 20°C was established, and a cooling zone at 35°C for 3
Drying was performed using dry air at 5% RH.

Composition of dye fixing element (4) Colloidal silica (1) manufactured by Nissan Chemical; Snowtex C Next, 0.06 g/n of kappa force laginan (0.06 g/n) was added to the third layer of the dye fixing element (1). A dye fixing element (5) was prepared.

Furthermore, as shown in the table below, one layer is added to the dye fixing element (6
)It was created.

In addition, the coating liquid film thickness from the first layer to the fourth layer was 6d.
/rrl', 35d/rrl', 6-/resistant, 15-/d
It was applied using a simultaneous multilayer coating method.

After coating, a 10 m cooling zone at 20°C was established and the temperature was increased to 35°C1.
Drying was performed using dry air at 35% RH.

Dye-fixing element (6) The following treatments were carried out using the above photosensitive element and dye-fixing element.

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

Next, this exposed photosensitive element is fed at a linear speed of 20 mm/sec, so that the emulsion surface is coated with 15 J/rr? of water is supplied with a wire bar, and immediately after that, the dye fixing elements (4) to (6
) and the membrane surfaces were placed in contact with each other. When heated for 15 seconds using a heat roller whose temperature was adjusted to 85°C, which is the temperature of the film surface that absorbed water, and peeled it off from the dye fixing element,
A clear image of the clay was obtained on the dye fixing element.

The obtained image shows that, in response to the unevenness of the drying air volume after application,
Density unevenness of 5 anal pitches occurred parallel to the application direction.

The average density of each of Y (yellow), M (macenta), and Cy (cyan) in the gray part is 1. The results of measuring the density unevenness in the 0 portion by microdensitometry (beam diameter 2 mfl+) are shown in the following table.

Furthermore, the number of white spots with a diameter of 3InI11 or more occurring in the image is shown.

As is clear from the above table, according to the present invention, in a dye fixing element having a dye fixing layer containing a mordant and a layer containing at least a natural polymer polysaccharide derived from red algae, the dye fixing layer and the natural polymer polysaccharide By having at least one layer between the layer containing the mordant and the hydrophilic binder that does not contain the natural polymeric polysaccharide, coating unevenness is significantly improved and an image without uneven white spots can be obtained. That is clear.

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

Similar results were also obtained when the dye fixing element polyethylene terephthalate was replaced with the following support (4) and the back layer was omitted.

Configuration of support (4)

Claims (2)

[Claims] (1) A dye fixing element having a dye fixing layer containing a mordant for fixing a mobile dye imagewise distributed on a support and a layer containing at least a natural polymeric 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 containing the natural polymer polysaccharide. (2) The pigment according to claim 1, wherein the natural polymeric polysaccharide derived from red algae is a natural polymeric polysaccharide selected from agar, kappa carrageenan, lambda carrageenan, iota carrageenan, and farcellan. Fixed element.