JPH0695197B2 - Photo elements - Google Patents

Description

Description: FIELD OF THE INVENTION This invention relates to photographic elements and, more particularly, to novel polymers which are good mordants for dyes used in photographic elements and photographic elements employing same.

More particularly, it relates to mordants for fixing imagewise generated diffusible dyes, and color photographic elements using layers containing the novel mordants.

(Prior Art) In the field of prior art, US Pat. Nos. 3,709,690, 3,958,995 and 3,89 have been used for immobilizing anionic dyes.
As described in the specification of 8,088 and the like, it is known to use a polymer having a quaternary ammonium salt as a side chain as a mordant. However, while this type of polymer exhibits good mordability to dyes, it lacks the ability to hold mordant dyes in a stable form. That is, a photographic system including a dye image mordanted with this type of mordanting agent has a drawback that the mordanted dye image is liable to undergo a chemical change or decomposition upon irradiation with a fluorescent lamp or sunlight.

The polymer mordant is usually used by coating it on a support or another coating film using a hydrophilic colloid such as gelatin as a binder. However, a coating film having this type of polymer mordant and a hydrophilic colloid exhibits significantly different mechanical properties as compared with a coating film formed by a hydrophilic colloid alone. That is, it has been found that a mixed film of a polymer mordant and gelatin, for example, has a significantly reduced tensile strength and breaking elongation as compared with a film of gelatin alone, resulting in a brittle film. The deterioration of the brittleness of the coating film is
This causes cracks due to thermal and mechanical strains that occur in the film coating process and drying process, and significantly restricts manufacturing conditions such as coating and drying.

It has also been found that the mordant layer in the dye-fixing element causes layer breakage (cracking) when thermal and mechanical strain is applied during handling of the dye-fixing element.

When the image forming method is carried out by using such a cracked dye-fixing element, unevenness may occur in the development and / or the transfer of the dye, or a cut may appear in the image, The image quality deteriorates significantly.

(Object of the Invention) Accordingly, an object of the present invention is to provide a mordant having excellent mordability and capable of retaining a mordant dye in a stable form to light, and a photographic element using the mordant.

It is also an object of the present invention to provide a photographic element having a mordant layer which resists cracking.

(Structure of the Invention) An object of the present invention is to provide at least one repeating unit represented by the general formula [I], a general formula [II] and a general formula [III].
This is accomplished by a photographic element containing a polymer having as a constituent at least one of the repeating units selected from

General formula [I] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 6 carbon atoms),
It may be linear or branched. L represents a divalent linking group (preferably having 1 to 20 carbon atoms). p represents 0 or 1. ) General formula [II] General formula (III) (In the formula, R ₅ and R ₈ each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 6 carbon atoms). R ₆ and R ′
₆ , R ″ ₆ represents a divalent hydrocarbon. R ₇ , R ′ ₇ , and R ″ ₇ represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), an aryl group (preferably having 6 to 6 carbon atoms). 20) or an aralkyl group (preferably having 7 to 20 carbon atoms). However, the alkyl group may be linear or branched. X, X ′, X ″ represents a divalent linking group. L, l ′, l ′ and m, m ′, m ″ each independently represent 0 or 1, and n, n ′ represents 2 to 30. Represents
q represents 0 to 30. Hereinafter, general formulas [I], [II] and [III] will be described in detail.

In the general formula [I], R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, n-
It represents a butyl group, an n-amyl group, an n-hexyl group or the like, and a hydrogen atom or a methyl group or an ethyl group is particularly preferable.

L is a divalent linking group having 1 to about 20 carbon atoms, for example, an alkylene group (eg, methylene group, ethylene group, trimethylene group, hexamethylene group, etc.), phenylene group (eg, o-phenylene group, p-phenylene group). Group, m-phenylene group, etc.), arylene alkylene group (eg, Such. However, R ₉ represents an alkylene group having 1 to 12 carbon atoms. ), —CO ₂ —, —CO ₂ —R ₁₀ — (wherein R ₁₀ represents an alkylene group, a phenylene group or an arylenealkylene group), (However, R ₁₁ represents an alkylene group, a phenylene group or an aralkylene group, and R ₁₂ represents a hydrogen atom, an alkyl group or a phenyl group.) And the like. Of these divalent linking groups, _{-CO 2 -, - CONH -,} - CO 2 -CH 2 CH 2 -, - CO 2 -CH 2 CH 2 C
H ₂ −, −CONHCH ₂ −, −CONHCH ₂ CH ₂ −, −CONHCH ₂ CH ₂ CH ₂
And the like are particularly preferable.

Preferred specific examples of the monomer unit represented by the general formula [I] of the present invention are shown below. However, it is not limited to these.

In formulas [II] and [III], R ₅ and R ₈ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, etc.).

R ₆ , R ′ ₆ and R ′ ₆ represent a divalent hydrocarbon, and typical examples thereof include an alkylene group having 1 to 10 carbon atoms (eg, methylene group, ethylene group, propylene group, 2,2 -Dimethyl-
1,3-propylene group, 2,2-dimethyl-1,6-hexylene group, etc.), arylene group having 6 to 12 carbon atoms (eg, phenylene group, naphthalene group, xylene group), 7 carbon atoms
15 aralkylene groups (eg, phenylene methylene group), cycloalkylene groups having 4 to 12 carbon atoms (eg,
A cyclobutylene group, a cyclohexylene group, etc.). R ₆
As preferred are alkylene groups and arylene groups,
More preferably, it is an alkylene group.

R ₇ , R ′ ₇ , R ″ ₇ are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms (for example, methyl group, ethyl group, n-butyl group, i-
Butyl group, t-butyl group, 2-ethylhexyl group, tridecyl group, etc.), aryl group having 6 to 20 carbon atoms (eg,
(Phenyl group, 4-methylphenyl group, 4-t-butylphenyl group, 4-methoxyphenyl group, etc.) or C7
~ 20 aralkyl groups (eg phenylmethyl group etc.)
Represents R ₇ , R ′ ₇ and R ″ ₇ are preferably a hydrogen atom, an alkyl group and a phenyl group, and more preferably an alkyl group.

X, X ', X "represents a divalent linking group, representative -R ₁₃ -O Examples _{-, - R 13 -COO -,} - R 13 OCO -, - R 13 -O-
R ₁₄ -O-, _{-O-R 13 -O -, -} R 13 -OCO-R 14 -COO- in which. Here, R ₁₃ and R ₁₄ are each independently an alkylene group (for example, a methylene group, an ethylene group, a propylene group, 2,2-
Dimethyl-1,3-propylene group, etc.), an arylene group (for example, a phenylene group, a naphthalene group, a xylene group, etc.) or an aralkylene group (for example, a phenylenemethylene group, etc.) is represented, and R ₁₅ is a hydrogen atom, an alkyl group ( For example, a methyl group, an ethyl group, a propyl group, etc.) or R ₆ OmR ₇ is represented.

l, l ′, l ″ and m, m ′, m ″ are each independently 0 or 1
, N and n'represent 2 to 30, and q represents 0 to 30. Particularly, n and n'are preferably 3 to 30, more preferably 4 to 30.

Of the general formula [III], the repeating unit of the following general formula [IV] is particularly preferable.

General formula (IV) In the formula, R ⁸ , X ′, R ′ ₆ , R ′ ₇ , l ′, m ′ and n ′ are the same as above.

Preferred specific examples of the monomer units represented by the general formulas [II] and [III] are shown below. However, it is not limited to these.

Such.

The polymers of the present invention have the general formulas [I], [II] and [II]
I] may be included, and preferable monomer units include, for example, acrylic acid esters (for example, n-butyl acrylate), methacrylic acid esters (for example, n-butyl methacrylate), acrylamides (for example, diacetone). Examples thereof include acrylamide), methacrylamides (eg, n-butylmethacrylamide), styrenes (eg, styrene sulfinic acid), and the like. Further, JP-A-60-122940 and JP-A-60-235134
It may contain a comonomer unit described in Japanese Patent Application No. 59-169042 and the like.

In the polymer of the present invention, the monomer unit represented by the general formula [I] is 10 to 95 mol% of all the monomers, preferably 40
Is 90 mol%, and the monomer unit represented by the general formula [II] or [III] is 2 to 70 mol%, preferably 5 to 50 mol% of all monomers. As the monomer units represented by the general formulas [I], [II] and [III], two or more kinds of monomer units may be used. Further, the polymer of the present invention may contain monomer units other than those represented by the general formulas [I], [II] and [III], but preferably the general formulas [I], [I]
The proportion of monomer units other than I] and [III] is 30 mol% or less of all monomers.

The polymer of the present invention preferably has a molecular weight of 5 × 10 ³ to 1 × 10 ⁷ . If the molecular weight is too small, the polymer may easily move, and if the molecular weight is too large, coating may be hindered. A more preferable molecular weight is 1 × 10 ⁴ to 2 × 10 ⁶ .

Preferred specific examples of the polymer used in the present invention are shown below, but the present invention is not limited thereto.

Next, the synthetic method of the polymer used in the present invention is shown.

Synthesis Example 1 Synthesis of poly (1-vinyl imidazole-co-pentaethylene glycol methyl vinyl ether) (P-1): 1-vinyl imidazole 44.
0g, pentaethylene glycol methyl vinyl ether 5
6.0 g and 300 ml of ethanol were added, the atmosphere was sufficiently replaced with nitrogen gas, and the mixture was heated to 75 ° C. When the temperature becomes constant, 2,
2'-Azobis (2,4-dimethylvaleronitrile) 1.242g
Was added and, while continuing heating, 1.242 g of the same 2,2'-azobis (2,4-dimethylvaleronitrile) was added after 2 hours. After continuing heating for 3 hours, the reaction sample was cooled to room temperature, put in a cellulose tube, dialyzed with tap water for 2 days, and freeze-dried to obtain 78.2 g of a polymer.

Synthesis Example 2 Synthesis of poly (1-vinylimidazole-co-α-methyltetraethylene glycol vinyl acetate) (P-7): 1-vinylimidazole 18. in a 300 ml three-necked flask.
7 g, α-methyltetraethylene glycol vinyl acetate 3
1.3 g and 150.0 g of dimethylformamide were added, the atmosphere was sufficiently replaced with nitrogen gas, and the mixture was heated to 70 ° C. When the temperature became constant, 2,2'-azobis (2,4-dimethylvaleronitrile) 0.
Add 615g and after 2 hours and 4 hours with continued heating 2,
2'-Azobis (2,4-dimethylvaleronitrile) 0.615g
Was further added. After that, heating was continued for 3 hours. After cooling the reaction sample to room temperature, add it to acetone 1.5 and dry it under vacuum.
1.6 g of polymer was obtained.

Synthesis Example 3 Synthesis of poly (1-vinylimidazole-co-α-methylnonaethylene glycol acetate vinyl-co-styrene sulfinic acid potassium salt) (P-8): 1-vinylimidazole 51.
2 g, α-methylnonaethylene glycol vinyl acetate 34.8
g, 14.0 g of potassium styrene sulfinate, and 300 g of distilled water were added, the atmosphere was sufficiently replaced with nitrogen gas, and the mixture was heated to 75 ° C. When the temperature became constant, 0.904 g of 2,2'-azobis (2-amidinopropane) hydrochloride was added, and 2,2'-azobis (2-amidinopropane) hydrochloride was added after 2 hours and 4 hours while continuing heating. An additional 0.904 g of chloride was added.
After that, heating was continued for 3 hours. After cooling the reaction sample to room temperature, 390 g of an aqueous polymer solution was obtained.

The polymeric mordants of this invention are used alone or in combination with a binder in the mordant layer in the photographic element. A hydrophilic binder can be used for this binder.
As the hydrophilic binder, a transparent or translucent hydrophilic colloid is typical, and examples thereof include proteins such as gelatin and gelatin derivatives, cellulose derivatives, starch, natural substances such as polysaccharides such as gum arabic, polyvinyl alcohol and polyvinyl. Includes synthetic polymers such as pyrrolidone and polyacrylamide.

Of these, gelatin and polyvinyl alcohol are particularly preferable.

This mordant layer may be provided in the light-sensitive material or in the dye fixing material for the color diffusion transfer method or the heat development photographic method.

The mixing ratio of the polymer mordant and the binder of the present invention and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of the dye to be mordant, the type and composition of the polymer mordant, and the image forming method applied. It can be determined, but the mordant / binder ratio is 20 / 80-80 / 20 (weight ratio),
The coating amount of the mordant is suitably from about 0.2 to about 15 g / m ^2, preferably used in inter alia 0.5 to 8 g / m ^2.

The mordant layer containing the polymer mordant of the present invention may contain various surfactants for the purpose of enhancing coatability.

Further, in the polymer mordant of the present invention, a gelatin hardener can be used in combination in the mordant layer.

Examples of gelatin hardeners that can be used in the present invention include:
For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds [1,3,5- Triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-ethylene-bis (vinylsulfonylacetamide), N, N'-trimethylene-bis (vinylsulfonylacetamide), etc.] , Active halogen compounds (2,4-dichloro-6-hydroxy-s
-Triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloacid, etc.), epoxy compounds, isoxazoles, dialdehyde starch, 1-chloro-6-hydroxytriazinylated gelatin, and the like. I can. A specific example is U.S. Pat. No. 1,870,354.
No., No. 2,080,019, No. 2,726,162, No. 2,870,013,
2,983,611, 2,992,109, 3,047,394, 3,0
57,723, 3,103,437, 3,321,313, 3,325,28
No. 7, No. 3,362,827, No. 3,490,911, No. 3,539,644,
3,543,292, British Patents 676,628, 825,544,
1,270,578, German Patent 872,153, 1,090,427,
No. 2,749,260, Japanese Patent Publication No. 34-7133, No. 46-1872, etc.

Among these gelatin hardeners, especially aldehydes, active vinyl compounds, active halogen compounds, Japanese Patent Application No. 60-2310
The epoxy compounds described in No. 93 are preferable.

These hardeners may be added directly to the mordant layer coating solution, or may be added to another coating solution so as to diffuse into the mordant layer during the process of multilayer coating.

The amount of the gelatin hardener used in the present invention can be arbitrarily selected according to the purpose. Usually, about 0.1 to about 50 wt% of gelatin used is suitable, preferably 1 to 30 w.
t%.

The polymer mordant of the present invention can be used in combination with a metal ion in a dye fixing material (element) to increase the transfer density of the dye. This metal ion can be added to a mordant layer containing a mordant or a layer adjacent thereto (either on the side closer to the support carrying the mordant layer or on the side farther from the support). The metal ion used here is preferably colorless and stable to heat and light. Ie C
Multivalent ions of transition metals such as u ²⁺ , Zn ²⁺ , Ni ²⁺ , Pt ²⁺ , Pd ²⁺ and Co ³⁺ ions are preferable, and Zn ²⁺ is particularly preferable. This metal ion is usually added in the form of a water-soluble compound, for example, ZnSO ₄ , Zn (CH ₃ CO ₂ ) ₂ , and the amount of addition thereof is suitably about 0.01 to about 5 g / m ² , preferably 0.1 to 1.5g / m
^{Is 2} .

A hydrophilic polymer can be used as a binder in the layer to which these metal ions are added. As the hydrophilic binder, a transparent or translucent hydrophilic colloid as specifically listed above for the mordant layer is useful.

The image forming dyes mordanted in the photographic elements of the present invention include the following. That is, azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes and phthalocyanine dyes having anionic groups such as phenolic hydroxyl groups, sulfonamide groups, sulfonic acid groups and carboxyl groups.

The photographic element of the present invention is particularly advantageously used for fixing a diffusible dye in a color image forming method in which a diffusible dye is imagewise formed or released, and then diffused and then fixed.

In the color image forming method described above, a method of developing using a developer at a temperature near room temperature [color diffusion transfer method] (for example, described in Belgian Patent 757,959), heat development in a substantially water-free state [Heat development method] (for example, European Patent No. 76492A2 and JP-A Nos. 58-79247 and 59-218443)
No. 60-79709 and Japanese Patent Application No. 60-79709), and the photographic element of the present invention can be used in any of them.

The dye-providing substance useful in the above-mentioned color image forming method is represented by the following formula (V) and is used in combination with a silver halide emulsion.

Dy-Y (V) Here, Dy represents a dye portion (or a precursor portion thereof), and Y represents a substrate having a function of changing the diffusibility of the dye-donor substance (V) as a result of development.

Here, “diffusibility changes” means that (1) the dye-donor substance (V) is originally non-diffusible, and this changes to diffusible or a diffusible dye is released, Alternatively (2) means that the originally diffusible dye-donor substance (V) changes to non-diffusible. Further, this change may occur due to the oxidation of Y or the reduction thereof depending on the nature of Y.

As an example of “change in diffusivity” due to oxidation of Y,
p-sulfonamidonaphthols (including p-sulfonamidophenols: JP-A-48-33,826 and JP-A-53-50,7)
36, European Patent No. 76,492, for specific examples), o-
Sulfonamide phenols (including o-sulfonamide naphthols: JP-A-51-113,624 and JP-A-56-12642)
No. 56-16130, No. 56-16131, No. 57-4043, No.
57-650, US 4,053,312, and European Patent No. 76,492 for specific examples), hydroxysulfonamide heterocycles (JP-A-51-104,343, European Patent No. 76,492 for specific examples) , 3-sulfonamidoindoles (JP-A-51-104,343, JP-A-53-46,730, JP-A-54-130,122,
57-850,55, European Patent No. 76,492 for specific examples), α-sulfonamido ketones (JP-A-53-3819).
Nos. 54-48,534 and European Patent No. 76,492), and so-called dye-releasing redox substrates.

As another example, Y is a type in which a dye is released by an intramolecular nucleophilic attack after being oxidized, as disclosed in JP-A-57-20735 and JP-A-57-735.
Intramolecular assist type substrates described in No. 177148 are listed.

Another example is a substrate that releases a dye by an intramolecular ring-closing reaction under basic conditions, but does not substantially release the dye when Y is oxidized (JP-A-51-63,618). There is a specific example in the issue). Further, as a modified form of this, a substrate in which the isoxazolone ring undergoes ring rewinding by a nucleophile to release a dye is also useful (specific examples are described in JP-A Nos. 49-111,628 and 52-4819).

Another example is a substrate in which the dye moiety is released by dissociation of an acidic proton under basic conditions, but the dye is not substantially released when Y is oxidized (JP-A-53-69,033). No. 54-130927).

On the other hand, examples of the change in diffusivity due to reduction of Y include nitro compounds described in JP-A-53-110,827: JP-A-53-110,827, US Pat.
The quinone compound described in 4,358,525 can be mentioned. These are reduced by a reducing agent (which is referred to as an electron donor) which is not consumed in the development process and remains, and the dye is released by the resulting intramolecular attack of the nucleophilic group. As this modification, a quinone-type substrate in which the dye moiety is detached by dissociation of the acidic proton of the reductant is also useful (JP-A Nos. 54-130,927 and 56-56).
-164,342 has specific examples).

When a substrate whose diffusivity is changed by the above reduction is used, it is essential to use an appropriate reducing agent (electron donor) which mediates between the exposed silver halide and the dye-donating substance. Specific examples thereof are described in the above-mentioned publicly known materials. A substrate (referred to as LDA compound) in which an electron donor coexists in the substrate Y is also useful.

As another dye-donating substance, there can be used one that undergoes a redox reaction with a silver halide or an organic silver salt at a high temperature, and as a result, the mobility of the compound having a dye moiety is changed. It is described in Japanese Patent Application No. 58-39400.

Further, a dye-donor substance which releases a mobile dye upon reaction with silver ions in the light-sensitive material is described in Japanese Patent Application No. 58-55692.

The photographic element of the present invention can be used in combination with a light-sensitive element for a color diffusion transfer method which is developed using a processing solution at around room temperature, or can be used in combination with a photothermographic element which is developed by heating. .

The silver halide that can be used in the above photosensitive element is silver chloride,
It may be any of silver bromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.

Specifically, U.S. Pat.No. 4,500,626, column 50, Research
Dice Closure Magazine, June 1978, pages 9-10 (RD1702
9), Japanese Patent Application Nos. 59-228551, 60-225176, and 60-228.
Any of the silver halide emulsions described in No. 267 etc. can be used.

The silver halide emulsion used in the present invention may be either a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain. Further, it may be a so-called core shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. Further, in the present invention, a linear inversion emulsion in which an internal latent image type emulsion and a nucleating agent are combined can be used.

The silver halide emulsion may be used as it is without post-heating, but it is usually chemically sensitized before use. For the conventional emulsions for light-sensitive materials, known methods such as sulfur sensitization method, reduction sensitization method and noble metal sensitization method 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-58-126526 and JP-A-58-215644).

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

The silver halide used in the present invention may be spectrally ring-enhanced with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, sensitizing dyes described in JP-A Nos. 59-180550 and 60-140335, Research Disclosure June 1978, pages 12 to 13 (RD17029), and JP-A-60- −111239
And heat-decolorizing sensitizing dyes described in Japanese Patent Application No. 60-172967.

These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

A dye that does not have a spectral sensitizing effect by itself, or a substance that does not substantially absorb visible light, together with a sensitizing dye,
A substance exhibiting supersensitization may be contained in the emulsion (for example, U.S. Pat.Nos. 2,933,390, 3,635,721, 3,743,510,
No. 3,615,613, No. 3,615,641, No. 3,617,295, No. 3,6
No. 35,721).

These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after chemical ripening, and U.S. Pat.
No. 4,225,666, before or after nucleation of silver halide grains.

The addition amount is generally 10 ^-8 to 10 per mol of silver halide.
^-It is about ² mol.

The photographic elements of this invention can be provided on a support separate from the light-sensitive element or can be a film unit associated with the light-sensitive element.

A typical form of the film unit is a form in which the image receiving element and the photosensitive element described above are laminated on one transparent support, and it is not necessary to peel the photosensitive element from the image receiving element after the completion of the transferred image. Is. More specifically, the image-receiving 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-donor substance for each emulsion layer, A combination of a magenta dye-donating substance and a cyan dye-donating substance (here, "an infrared light-sensitive emulsion layer is an emulsion layer sensitive to light of 700 nm or more, especially 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 layer containing the dye-donating substance so that the transferred image can be viewed through the transparent support. Complete development in the light A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer for the purpose of enabling the light-sensitive element, and if necessary, at a suitable position so that all or a part of the light-sensitive element can be separated from the image-receiving element. A release layer may be provided (such an embodiment is described, for example, in JP-A-56-67840 and Canadian Patent 674,082).

Further, in another form in which peeling is not required, the above-mentioned photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. A mode in which an image receiving element, a white reflective layer, a peeling layer and a photosensitive element are laminated on the same support, and a mode in which the photosensitive element is intentionally peeled from the image receiving element is described in US Pat. No. 3,730,718. On the other hand, there are roughly two representative forms in which a light-sensitive element and an image-receiving element are separately coated on two supports, one is a peeling type and the other is a peeling-free type. In more detail, in a preferable embodiment of the peelable film unit, the support has a light-reflective layer on the back surface thereof, and at least one image-receiving layer is coated on the surface thereof. The photosensitive element is coated on a support having a light-shielding layer, and the photosensitive layer-coated surface and the mordant layer-coated surface do not face each other before the exposure is completed, but after the exposure is completed (for example, during development processing), the photosensitive layer is exposed. It is designed so that the coated surface is scratched back and overlaps with the coated surface of the image receiving layer. After the transfer image is completed on the mordant layer, the light-sensitive element is rapidly separated from the image-receiving element.

In a preferred embodiment of the peel-free type 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-shielding layer. The photosensitive layer coated surface and the mordant layer coated surface face each other and are superposed.

Any of the above-mentioned forms can be applied to both the color diffusion transfer system and the heat development system. In the former case, however, a pressure-rupturable container (processing element) containing an alkaline processing liquid is further combined. May be. In particular, in a peel-free type film unit in which an image receiving element and a photosensitive element are laminated on one support, this processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. Further, in the form in which the light-sensitive element and the image-receiving element are separately coated on the two supports, it is preferable that the processing element is disposed between the light-sensitive element and the image-receiving element at the latest during the development processing. The processing element preferably contains a light-shielding agent (such as carbon black or a dye whose color changes depending on pH) and / or a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the color diffusion transfer type film unit, it is preferable that a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element or the photosensitive element.

On the other hand, in the case of a heat developing type film unit, a heat generating layer containing metal fine particles, conductive particles such as carbon black or graphite is provided at an appropriate position of a support, a light-sensitive element or an image receiving element to allow heat development or For the diffusion transfer of the dye, it is possible to utilize the heat generated from electricity when electricity is applied. A semiconductor inorganic material (for example, silicon carbide, molybdenum silicide, lanthanum chloride, barium titanate ceramics, tin oxide, zinc oxide, etc.) may be used instead of the conductive particles.

The case where the present invention is applied to a photothermographic material will be described below.

When the present invention is applied to a photothermographic material, an organic metal salt may be used as an oxidizing agent together with silver halide. In this case, the photosensitive silver halide and the organic metal salt need to be in contact with each other or in a close distance.

Among such organic metal salts, organic silver salts are particularly preferably used.

Examples of the organic compound that can be used to form the above organic silver salt oxidizing agent include compounds described in Japanese Patent Application No. 59-228551, pages 37 to 39, U.S. Patent 4,500,626, columns 52 to 53, etc. Get up. Further, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolic acid described in Japanese Patent Application No. 60-113235 and silver acetylene described in Japanese Patent Application No. 60-90089 are also useful. Two or more kinds of organic silver salts may be used in combination.

The above organic silver salts are the following per mol of photosensitive silver halide:
0.01 to 10 mol, preferably 0.01 to 1 mol can be used in combination. The total coating amount of the light-sensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ^{2 in} terms of silver lees.

The above-mentioned dye-donor compounds and hydrophobic additives such as image-forming accelerators described below can be incorporated into the layers of the light-sensitive element by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
59-178451, 59-178452, 59-178453,
59-178454, 59-178455, 59-178457, such as a high-boiling organic solvent, as described in the boiling point 50 ℃
It can be used in combination with an organic solvent having a low boiling point of up to 160 ° C.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, with respect to 1 g of the dye-donor substance used.

Further, 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, fine particles can be dispersed and contained in a binder in addition to the above method.

When dispersing the hydrophobic substance in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-15
The surfactants listed on pages (37) to (38) of 7636 can be used.

In the present invention, it is desirable that the light-sensitive element contains a reducing substance. Examples of the reducing substance include those generally known as a reducing agent, and the dye-donating substance having the above-described reducing property. Further, a reducing agent precursor which does not have reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process is also included.

Examples of reducing agents used in the present invention include US Pat.
0,626, columns 49-50, 4,483,914, columns 30-31, JP-A-60-140335, pages (17)-(18), JP-A-60-12.
8438, 60-128436, 60-128439, 60-1284
The reducing agents described in No. 37 etc. can be used. In addition, JP-A-56-
The reducing agent precursors described in 138,736, 57-40,245 and U.S. Pat. No. 4,330,617 can also be used.

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

In the present invention, the amount of reducing agent added is 0.
The amount is 01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive element. For specific compounds that are preferably used, see US Pat.
No. 6 columns 51-52.

Various antifoggants or photographic stabilizers can be used in the present invention. For example, research
The azoles and azaindenes described in December 1978, pages 24 to 25 of Deice Closure Magazine, carboxylic acids and phosphoric acids containing nitrogen described in JP-A-59-168442, or JP-A-59-111636. The mercapto compound and its metal salt, and the acetylene compounds described in Japanese Patent Application No. 60-228267 are used.

In the present invention, the light-sensitive element may contain an image toning agent, if necessary. Specific examples of effective toning agents include compounds described in Japanese Patent Application No. 59-268926, pages 92 to 93.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, it is necessary to use a light-sensitive element having at least three silver halide emulsion layers having light-sensitivity in different spectral regions. Good. For example, the blue layer,
A combination of three layers of green-sensitive layer and red-sensitive layer, green-sensitive layer, red-sensitive layer,
There are combinations of infrared photosensitive layers. Each of these photosensitive layers may be divided into two or more layers if necessary.

The photosensitive element used in the present invention is, if necessary, various additives known for heat-developable photosensitive elements, and layers other than the photosensitive layer, such as a protective layer, an intermediate layer, an antistatic layer, an antihalation layer, and a dye. It may have a release layer, a matte layer or the like to facilitate the release from the fixing element. Examples of various additives include plasticizers, matting agents, sharpness-improving dyes, and anti-halation agents described in Research Disclosure, June 1978, pages 9 to 15 and Japanese Patent Application No. 59-209563. There are additives such as dyes, surfactants, optical brighteners, anti-slip agents, oxide rod materials, and anti-fading agents.

In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and an ultraviolet absorber. The protective layer and the intermediate layer may each be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent for preventing discoloration or color mixture, an ultraviolet absorber, or a white pigment such as titanium dioxide. The white pigment may be added to the emulsion layer as well as the intermediate layer for the purpose of improving the sensitivity.

If necessary, the image-receiving element (hereinafter referred to as the dye-fixing element) can be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer.
One or more of the above layers may include hydrophilic thermal solvents, plasticizers, anti-fading agents, UV absorbers, slip agents, matting agents, antioxidants, and dispersed vinyl to increase dimensional stability. A compound, a surfactant, an optical brightener, etc. may be included. Further, particularly in a system in which heat development and transfer of a dye are simultaneously performed in the presence of a small amount of water, it is preferable to include a base and / or a base breaker described below in the dye fixing element in the sense that the storage stability of the sensitivity element is improved. . Specific examples of these additives are described on pages 101 to 120 of Japanese Patent Application No. 59-209563.

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details of these are described in Japanese Patent Application No. 59-213978, pp. 67-71.

In addition to this, there are various methods for generating a base, and any compound used in the method is useful as a base breaker. For example, a method in which a base is generated by mixing a sparingly soluble metal compound described in Japanese Patent Application No. 60-169585 and a compound capable of complexing reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound). Alternatively, there is a method of generating a base by electrolysis as described in Japanese Patent Application No. 60-74702.

The former method is particularly effective. Examples of the sparingly soluble metal compound include carbonates, hydroxides, oxides and the like of zinc, aluminum, calcium, barium and the like. Regarding complex-forming compounds, for example, co-authored by A.E. Martell and A.M.
"Critical Stability Constants (Critic
al Stability Constants ”, Volumes 4 and 5, Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acids, pyridylcarboxylic acids, aminophosphoric acids, carboxylic acids (mono, di,
Tri, tetracarboxylic acids and further phosphono,
Hydroxy, oxo, ester, amide, alkoxy,
Compounds with substituents such as mercapto, alkylthio, phosphino), hydroxamic acids, polyacrylates, polyphosphoric acids, etc. and alkali metals, guanidines,
Examples thereof include salts with amidines and quaternary ammonium salts.

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 light-sensitive element and / or the dye-fixing element of the present invention, various development terminators can be used for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development.

The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof (for example, Japanese Patent Application No. 58-216928, 59-48305, 59-8
5834 or 59-85836, etc.).

Further, a compound which releases a mercapto compound by heating is also useful, for example, Japanese Patent Application Nos. 59-190173 and 59-268926.
No. 59-246468, No. 60-26038, No. 60-2602,
60-26039, 60-24665, 60-29892, 59
-176350, there is a compound described.

A hydrophilic binder may be used as the binder of the photosensitive element and / or the dye fixing element of the present invention. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical, and for example, gelatin, proteins such as gelatin derivatives, cellulose derivatives, starch, natural substances such as polysaccharides such as arabic gum, and polyvinylpyrrolidone,
Includes synthetic polymeric materials such as water soluble polyvinyl compounds such as acrylamide polymers. It is also possible to use a dispersed vinyl compound which is used in the form of a latex and increases the dimensional stability of the photographic material. These binders can be used alone or in combination.

In the present invention, the binder is applied in an amount of 20 g or less per 1 m ² , preferably 10 g or less, more preferably 7 g or less.

The ratio of the high-boiling organic solvent and the binder dispersed together with the hydrophobic compound such as the dye-providing substance in the binder is 1 cc or less of the solvent per 1 g of the binder, preferably 0.5 cc or less, and more preferably 0.3 cc or less. is there.

The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive element and / or dye fixing element of the present invention may contain an inorganic or organic hardener.

Specific examples of the hardener include those described in Japanese Patent Application No. 59-268926, pages 94 to 95 and JP-A-59-157636, page (38), which may be used alone or in combination. Can be used.

In order to promote dye transfer, a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature may be incorporated in the photosensitive element or the dye fixing element. The hydrophilic thermal solvent may be incorporated in either the photosensitive element or the dye fixing element, or may be incorporated in both. The built-in layer may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer.
Alternatively, it is preferably incorporated in the adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. Further, a high-boiling point organic solvent may be contained in the light-sensitive element and / or the dye-fixing element in order to promote dye transfer.

The support used in the light-sensitive element and / or the dye-fixing element of the present invention can withstand the processing temperature.
As a general support, not only glass, paper, polymer film, metal and its analogues are used,
The support described on pages 95 to 96 of Japanese Patent Application No. 59-268926 can be used.

The light-sensitive element and / or the dye-fixing element may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of dye.

In this case, the transparent or opaque heating element can be manufactured by using a conventionally known technique as a resistance heating element. As the resistance heating element, there are a method of using a thin film of an inorganic material showing a semiconductor and a method of using an organic thin film in which conductive fine particles are dispersed in a binder. Materials usable in these methods include those described in Japanese Patent Application No. 59-151815.

In the present invention, as the coating method for the photothermographic layer, protective layer, intermediate layer, undercoat layer, backing layer, dye fixing layer and other layers, the methods described in US Pat. No. 4,500,626, columns 55 to 56 can be applied.

Radiation that also contains visible light can be used as a light source for image exposure for recording an image on the photosensitive element. Generally, light sources used for ordinary color printing, such as halogen lamps such as tungsten lamps, mercury lamps, iodine lamps, xenon lamps, laser light sources, CRT light sources,
The light sources such as light emitting diodes (LEDs) described in Japanese Patent Application No. 59-268926, page 100 and US Pat. No. 4,500,626, column 55 can be used.

In the present invention, the steps of heat development and dye transfer may be independent or simultaneous. Further, continuous transfer may be performed in the sense that the scratch transfer is performed for the development in one step.

For example, (1) after imagewise exposing the photosensitive element and heating,
There is a method of stacking dye-fixing elements and heating as necessary to transfer the movable positive dye to the dye-fixing element, and (2) a method of exposing the photosensitive element to an image and exposing and stacking the dye-fixing elements.
The above methods (1) and (2) can be carried out in the substantially absence of water, or can be carried out in the presence of a trace amount of water.

The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but about 80 ° C. to about 180 ° C. is particularly useful. When heating in the presence of a trace amount of water, the upper limit of the heating temperature is the boiling point or lower. When the transfer step is carried out after the completion of the heat development step, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but especially at 50 ° C or higher, about 10 ° C higher than the temperature in the heat development step. Up to a lower temperature is more preferable.

In the present invention, the preferred image forming method is heating in the presence of a trace amount of water and a base and / or a base precursor after or at the same time as the image exposure, and at the same time as the development, the diffusion generated in the portion corresponding to or inversely corresponding to the silver image. The sex dye is transferred to the dye fixing layer. According to this method
The generation or release reaction of the diffusible dye proceeds extremely quickly,
The migration of the diffusible dye to the dye-fixing layer also progresses rapidly, so that a high-density color image can be obtained in a short time.

The amount of water used in this embodiment is at least 0.1 times the weight of the total coating film of the light-sensitive element and the dye-fixing element, preferably 0.1.
It may be as small as or more than twice the weight of the solvent corresponding to the maximum swelling volume of the entire coated film (particularly less than or equal to the weight of the solvent corresponding to the maximum swelling volume of the entire coated film minus the weight of the entire coated film).

The state of the film during swelling is unstable, and local bleeding may occur under certain conditions.To avoid this, the total coating thickness of the photosensitive element and dye fixing element corresponds to the maximum swelling volume. It is preferably less than or equal to the amount of water used. Specifically, the total area of the photosensitive element and the dye fixing element is 1 g to 50 per 1 square meter.
The range of g, particularly 2 g to 35 g, and further 3 g to 25 g is preferable.

The base and / or base precursor used in this embodiment can be incorporated in both the light-sensitive element and the dye-fixing element. It can also be dissolved in water and supplied.

In the above aspect, the image-forming reaction system, as a base precursor, a water-insoluble basic metal compound and a metal ion constituting the hardly-soluble metal compound and a compound capable of a complex formation reaction in water as a medium, It is preferred to raise the pH of the system by the reaction of these two compounds on heating.
Here, the image reaction system means a region where an image forming reaction occurs. Specific examples include layers belonging to both the light-sensitive element and the dye-fixing element. When there are two or more layers, any of them may be used.

The sparingly soluble metal compound and the complex-forming compound must be added to at least another layer in order to prevent them from reacting before the development processing. For example, in a so-called monosheet material in which a light-sensitive element and a dye-fixing element are provided on the same support, it is preferable that the additive layers of the both are separate layers and that one or more layers are interposed therebetween. In addition, a more preferable form is
The sparingly soluble metal compound and the complex-forming compound are contained in layers provided on separate supports. For example, it is preferable that the poorly soluble metal compound is contained in the light-sensitive element and the complex-forming compound is contained in the dye-fixing element having a support different from that of the light-sensitive element. The complex-forming compound may be dissolved in water to be coexistent and supplied. The sparingly soluble metal compound is disclosed in JP-A-56-174830.
No. 53-102733, etc., and it is desirable to include it as a fine particle dispersion prepared by the method described in JP-A No. 53-102733. The average particle size thereof is preferably 50 microns or less, particularly preferably 5 microns or less. The sparingly soluble metal compound may be added to any layer of the photosensitive element such as the photosensitive layer, the intermediate layer and the protective layer, or may be added by dividing it into two or more layers.

The amount of the sparingly soluble metal compound or complex-forming compound to be added to the layer on the support depends on the compound species, the particle size of the sparingly soluble metal compound, the complex formation reaction rate, etc. It is suitable to use it in an amount of 50% by weight or less, more preferably 0.01% by weight to 40% by weight. When the complex-forming compound is dissolved in water and supplied, a concentration of 0.005 mol to 5 mol, and particularly 0.05 mol to 2 mol per liter is preferable. Furthermore, in the present invention, the content of the complex-forming compound in the reaction system is a molar ratio with respect to the content of the sparingly soluble compound.
It is preferably 1/100 to 100 times, particularly preferably 1/10 to 20 times.

As a method of applying water to the photosensitive layer or the dye fixing layer,
For example, there is a method described in Japanese Patent Application No. 59-268926, page 101, line 9 to page 102, line 4.

As a heating means in the developing and / or transferring process, a heating plate, an iron, a heating roller, or the like is disclosed in Japanese Patent Application No. 59-2689.
There are means described in No. 26, page 102, line 14 to page 103, line 11. Alternatively, a layer of a conductive material such as graphite, carbon black, or metal may be superposed on the light-sensitive element and / or the dye-fixing element, and an electric current may be passed through the conductive layer to directly heat the conductive layer. Good.

The pressure condition and the method of applying pressure when the photosensitive element and the dye fixing element are superposed and brought into close contact are described in Japanese Patent Application No. 59-268926.
The method described on pages 103 to 104 can be applied.

Any of a variety of thermal development apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-75247 and 59-1.
77547, 59-181353, 60-18951, Jpn.
The devices described in 116734 and the like are preferably used.

(Examples) Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention.

Example 1 A method for producing a benzotriazole silver emulsion will be described.

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 300 ml of water. The solution was kept at 40 ° C. and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes.

The pH of this benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Then, the pH was adjusted to 6.30 to obtain a benzotriazole silver emulsion with a yield of 400 g.

Next, how to make an acetylene silver emulsion will be described.

28 g of gelatin and 26.7 g of potassium 4-acetylaminophenylpropionate were dissolved in 500 ml of water. 40 this solution
The mixture was kept at ℃ and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes, and the mixture was further stirred for 10 minutes.

The pH of this emulsion was adjusted to 6.30 and the yield was 400 g by centrifugation.
To obtain a silver acetylene emulsion.

How to make silver halide emulsions for the fifth and first layers is described.

600 ml of an aqueous solution containing well-stirred gelatin aqueous solution (containing 1000 g of water containing 20 g of gelatin and 3 g of sodium chloride and kept at 75 ° C and kept at 75 ° C) and an aqueous solution of silver nitrate (600 ml of water and silver nitrate) 0.59 mol dissolved) was added simultaneously over 40 minutes at an equal flow rate. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 50 mol%) having an average grain size of 0.40 μm was prepared.

After washing with water and desalting, 5 ml of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, and chemical sensitization was performed at 60 ° C. Emulsion yield is 600g
It was.

Next, how to prepare a silver halide emulsion for the third layer will be described.

600 ml of an aqueous solution containing well-stirred gelatin aqueous solution (containing 1000 g of water containing 20 g of gelatin and 3 g of sodium chloride and kept at 75 ° C and kept at 75 ° C) and an aqueous solution of silver nitrate (600 ml of water and silver nitrate) 0.59 mol dissolved) was added simultaneously over 40 minutes at an equal flow rate. Thus, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, and chemical sensitization was performed at 60 ° C. Emulsion yield is 600g
It was.

Next, a method for preparing a gelatin dispersion of a dye-donor substance will be described.

5 g of the yellow dye-donor substance (A), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and 10 g of triisononyl phosphate were weighed and added with 30 ml of ethyl acetate. Dissolve by heating to 60 ℃,
A homogeneous solution was obtained. 10% of this solution and lime-processed gelatin
After mixing 100 g of the solution with stirring, the mixture was dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a yellow dye-donor substance dispersion.

Other than using the magenta dye-donating substance (B) and 7.5 g of tricresyl phosphate as the high boiling point solvent,
A magenta dye-donor dispersion was similarly prepared by the above method.

A cyan dye dispersion was prepared using the cyan dye-donor (C) in the same manner as the yellow dye dispersion.

From these, a color light-sensitive material having a multilayer structure as shown in the following table was produced.

Dye donating substance Sensitizing dye Reducing agent Next, how to make the dye fixing material will be described.

A dye fixing material [A] was prepared by coating on a polyethylene-laminated paper support in the constitution shown in the following table.

A tungsten light bulb is used for the above-mentioned multi-layered color light-sensitive material, and G, R, and IR three-color separation filters whose densities are continuously changed (G is 500 to 600 nm, R is 600 to 700 nm bandpass filter, IR is Exposure was carried out for 1 second at 500 lux through a filter having a transmission of 700 nm or more).

7 ml / m ² of water was supplied to the emulsion surface of the exposed light-sensitive material by a wire bar, and then the dye-fixing material [A] was superposed so that the film surface was in contact with it.

Using a heat roller whose temperature was adjusted so that the water-absorbed film had a temperature of 90 to 95 ° C., after heating for 20 seconds, the dye-fixing material was peeled off from the light-sensitive material, and the brittleness and photographic performance were examined, as shown in Table 1. I got good results.

The dye mordant HP-1 of the above dye fixing material [A] was replaced with the following mordant HP-2 and the polymer P-7, P-8, P-9, P-1 of the present invention.
Dye fixing material [B], [C], [D], [E] and [F] in the same manner as dye fixing material [A] except that 0 is used.
Made. Using these dye-fixing materials [B] to [F], the same operation as in the dye-fixing material [A] was carried out, and the brittleness and the photographic performance were examined.

As shown in Table 1, the mordants P-7, P-8, P-9,
It is clear that by using P-10, the evaluation value of brittleness becomes small while maintaining the maximum concentration, and the cracking is remarkably improved. It is also found that by using the mordant of the present invention, a mordability equal to or higher than the conventional one can be obtained. The dye image formed on the dye-fixing material of the present invention was stable even when exposed to light and heat for a long period of time.

(Effect of the Invention) According to the present invention, a mordant having excellent mordability and capable of stably retaining a mordant dye for a long period of time against light and wet heat was obtained. Further, the mordant layer according to the present invention has an effect that cracks are less likely to occur.

Claims (1)

[Claims] 1. A photographic element containing a polymer having as a constituent at least a repeating unit represented by the general formula [I] and a repeating unit selected from the general formula [II] and / or the general formula [III]. General formula [I] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group, and may be linear or branched.
L represents a divalent linking group. p represents 0 or 1. ) General formula [II] General formula (III) (In the formula, R ₅ and R ₈ each independently represent a hydrogen atom or an alkyl group. R ₆ , R ′ ₆ and R ″ ₆ represent divalent hydrocarbons. R ₇ , R ′ ₇ and R ″ ₇ Represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, provided that the alkyl group may be linear or branched. X, X ', X "represent a divalent linking group. ′, L ″ and m, m ′, m ″ each independently represent 0 or 1, n, n ′ represents 2 to 30, and q represents 0 to 30.
Represents )