JP2002062629A - Color diffusion transfer photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color diffusion transfer photographic sensitive material that does not cause image defects even when exposed to intense light immediately after processing at a low temperature and that produces a good image. SOLUTION: In the color diffusion transfer photographic sensitive material forming an image by spreading an alkaline processing composition between a photosensitive sheet with at least one silver halide emulsion layer on the base and a transparent cover sheet, a high molecular hardening agent is contained in at least one photographic constitutive layer situated farther from the base than the silver halide emulsion layer closest to the base in the photosensitive sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color diffusion transfer photographic light-sensitive material which does not require peeling and uses an alkaline processing composition.

[0002]

2. Description of the Related Art A color diffusion transfer photographic method using an azo dye image-forming substance which gives an azo dye having a diffusibility different from that of the image forming compound itself as a result of development under alkaline conditions has been well known. I have. Conventional color diffusion transfer photographic film units are roughly classified into a peeling type and a peeling-free type. In the peeling type, the photosensitive layer and the dye image-receiving layer are coated on separate supports, and after the image exposure, the photosensitive sheet and the dye-image receiving sheet are superimposed, and the processing liquid is developed during that time.
Thereafter, the dye receiving sheet is peeled off to terminate the processing. On the other hand, the peeling-free type has an alkali neutralizing function in the film unit, and neutralizes at a certain timing after developing the alkali treatment liquid,
The development processing and the dye transfer processing have been completed. As an example of the configuration of the film unit, a photosensitive sheet in which a dye image receiving layer, a white reflective layer, a light shielding layer, and a photosensitive layer combined with a dye forming substance are sequentially coated on a transparent support, and an alkali having a light shielding function, A film unit in which a treatment composition and a transparent cover sheet having a neutralization timing function are combined. After exposing the photosensitive layer of the photosensitive sheet to an image, an alkali treatment composition having a light shielding function is developed between the photosensitive sheet and the cover sheet, so that the color development reaction is performed and at the same time, the photosensitive layer is removed. The film unit is shielded from light, making it possible to handle the film unit in a light place. The color diffusion transfer film unit is used under various temperature conditions from indoor to outdoor, and a neutralization timing layer is used to compensate for the delay of development reaction and dye generation / diffusion at low temperature, and when the processing temperature is low Has been provided with a function of extending the alkali neutralization timing time, thereby stabilizing the image density. JP-A-6-308693, JP-A-7-128830 and JP-A-7-138225 disclose a method capable of maintaining a high color density even at a low processing temperature by using a photographic element for color diffusion transfer containing a specific sulfonamide compound. Attempts have been made to further expand the temperature range that is disclosed and that allows development. However, the inventors of the present invention have studied in detail that the problem that the light shielding function of the above-described alkali treatment composition is likely to be reduced particularly in a development process at a low temperature as the use temperature range is widened. It turned out. More specifically, if the film unit is exposed to strong light such as direct sunlight immediately after photographing and developing at a low temperature, a spot-like defect is likely to occur in a transferred image. Color diffusion transfer photographic light-sensitive materials are used in various photographing scenes, and it is required that a high-quality and stable image can be obtained regardless of a use temperature condition.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color diffusion transfer photographic light-sensitive material which does not cause image defects even when exposed to intense light immediately after processing at a low temperature so that a good image can be obtained. is there.

[0004]

The object of the present invention has been attained by the following (1) to (3). (1) A color diffusion transfer photographic light-sensitive material in which an image is formed by developing an alkaline processing composition between a light-sensitive sheet having at least one silver halide emulsion layer on a support and a transparent cover sheet. A color diffusion transfer photographic material comprising a polymer hardener in at least one of the photographic constituent layers located farther than the silver halide emulsion layer closest to the support in the sheet. (2) The photographic sheet according to (1), wherein a polymeric hardener is contained in a photographic component layer farthest from the support on the side of the silver halide emulsion layer with respect to the support in the photosensitive sheet. Color diffusion transfer photographic photosensitive material. (3) The color diffusion transfer photographic light-sensitive material as described in (1) or (2), wherein the polymer hardener is a polymer hardener having a vinyl sulfone structure.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the polymer hardener used in the present invention will be described. The polymer hardener used in the present invention must have diffusion resistance during and after the application of the photographic constituent layer, and has a number average molecular weight of 2,000 to 30,
It is preferably 10,000, and more preferably 10,000 to 100,000. A low molecular weight hardener having a number average molecular weight of less than 2,000 tends to diffuse from one gelatin layer to another in a multilayer coating as in the present invention, which does not meet the purpose of the present invention. The polymer hardener used in the present invention has a plurality of reactive groups in its molecule that bind and react with a hydrophilic colloid such as gelatin. The polymer hardener may or may not have a hydrophilic group in the molecule of the polymer hardener. When the polymer hardener is water-soluble, it can be added as an aqueous solution, and when it is insoluble in water, it can be added as an emulsified dispersion. As the polymer hardener used in the present invention, aldehyde, N-methylol, α-diketone, sulfonic acid ester, active halogen compound, s-triazine, epoxide, aziridine, active olefin, imide, carbodiimide, etc. (Hereinafter, also simply referred to as “mold”). In the present invention, "activity" refers to a state in which a chemical reaction is likely to occur,
Specifically, it means that it has reactivity with a hydrophilic colloid (such as gelatin) contained in the layer to which the polymer hardener used in the present invention is added. Also, The T
heavy of the Photographic
Process. 4th edition, page 84, polyvinyl alcohol or partially acetylated cellulose maleic acid half ester, glycidyl acrylate copolymer, acrolein-acrylic acid copolymer, amino acid polymer having chlorotriazine as a pendant, Bisulfite adducts of polyacrolein can also be used.

The polymer hardener used in the present invention comprises a polymer having a functional group capable of reacting with a hydrophilic colloid (eg, gelatin) contained in a layer to which the polymer hardener is added. And a hardening agent having a polymer having a functional group represented by the following formulas (1) to (9). Equation (1) -SO ₂ CH = CH ₂ Formula (2) -SO ₂ CH ₂ CH ₂ X formula (2), X represents a functional group represented by the formula (2) is reacted with nucleophiles or bases At the time of the reaction, a group (for example, —Cl, —OSO ₂ C)
_{H 3, -OSO 2 C 6 H} 4 CH 3, -OCOCH 3, -OSO
₃ ^- is a pyridinium, etc.). Equation (3)

[0007]

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In the formula (3), X is a single bond, -O-, -NR
And-represents a hydrogen atom, an alkyl group or an aralkyl group. Y and Z each represent a halogen atom (for example, a chlorine atom or a bromine atom), an alkoxy group (for example, methoxy), a hydroxyl group and a salt thereof, or an amino group which may be substituted, and at least one of Y and Z is a halogen atom . Formula (4) -CHO Formula (5)

[0009]

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Formula (6) -NCO Formula (7) -NHCONHCOCH = CH ₂ Formula (8) -NHCONHCOCH ₂ CH ₂ X In the formula, X has the same meaning as X in formula (2). Formula (9) -COX In the formula, X is a group which is easily eliminated when the functional group represented by the formula (9) reacts with an amino group (for example,

[0011]

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The formula (9) represents what is generally known as an active ester group or a mixed acid anhydride.

In producing the polymer hardener used in the present invention, the polymerization method is not particularly limited. For example, it may be produced by a polycondensation method, and a compound having an ethylenically unsaturated bond may be used. And may be produced by a method such as radical polymerization or anionic polymerization. Further, it may be produced by introducing the reactive group into a natural polymer (for example, starch, dextran, gelatin, etc.). Functional groups capable of reacting with the hydrophilic colloid used in the present invention (functional groups represented by the above formulas (1) to (9), hereinafter referred to as reactive functional groups)
There is also no particular limitation on the method of introduction, and a polymer may be produced by performing a polymerization reaction using a monomer having a reactive functional group, or the polymer may be produced in advance by a so-called polymer reaction after producing the polymer. A reactive functional group may be introduced.
Further, a method of performing a polymerization reaction using a monomer compound having a precursor of a reactive functional group, and then generating a reactive functional group by an appropriate method is also effective.

The polymer hardener used in the present invention is preferably produced by radical polymerization of a monomer having a reactive functional group (or a precursor thereof) and an ethylenically unsaturated bond in the same molecule. Is done. The following compounds are typical examples of the monomer having a reactive functional group.

[0015]

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[0016]

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[0017]

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The polymer used in the present invention may be a homopolymer of a monomer having a reactive group, or may be a copolymer with one or more other monomers. In the case of a copolymer, the proportion of the monomer having a reactive group is 1% by mass or more, preferably 5% by mass or more. In the case of radical copolymerization, other monomers are not particularly limited as long as radical polymerization is possible, but the following monomers can be mentioned as specific examples. When the other monomer has a functional group capable of reacting, the functional group represented by the formulas (1) to (9) is not reacted with the functional group at the time of copolymerization.
It is preferable to appropriately select a combination of monomers.

Acrylic acid, methacrylic acid and esters thereof: for example, acrylic acid, methyl acrylate, butyl acrylate, benzyl acrylate, hydroxyethyl acrylate, CH ₂ ＣＨCHCOO (CH ₂ CH ₂
O) _n R (R is a hydrogen atom, an alkyl group, n is an integer of 1 or more), methacrylic acid, methyl methacrylate, ethyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, N Amides of ethylenically unsaturated carboxylic acids: acrylamide, methacrylamide, N-acryloyl morpholine, N-dimethylaminoethyl methacrylate, 2-sulfoethyl methacrylate, etc.
N, N-dimethylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid (or salt thereof)
Aromatic monomers: styrene, vinyltoluene, pt-butylstyrene, p-vinylbenzoic acid, vinylnaphthalene, etc. Other vinyl monomers: ethylene, propylene, vinyl chloride, vinylidene chloride, trifluoroethylene , Trifluorochloroethylene, vinyl acetate, vinyl propionate,
Vinyl alcohol, N-vinylpyrrolidone, N-vinylacetamide, acrylonitrile, methacrylonitrile and the like.

Specific examples of the polymer hardener used in the present invention are shown below (number average molecular weight: 20,000 to 60,000), but the present invention is not limited to these. The copolymerization ratio of each compound represents a mass percentage ratio.

P-1 M-1 / 2-acrylamide-2
-Methyl propanesulfonic acid sodium copolymer (10/9
0) P-2 M-1 / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (30/70) P-3 M-1 / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (30/70) 50/50) P-4 M-1 / methyl methacrylate copolymer (20
/ 80) P-5 M-2 / sodium acrylate copolymer (30/7
0) P-6 M-2 / 2-hydroxyethyl methacrylate copolymer (20/80) P-7 M-3 / butyl acrylate copolymer (60 /
40) P-8 M-4 / 2-acrylamide-2-methylpropanesulfonic acid sodium copolymer (30/70) P-9 M-6 / ethyl acrylate copolymer (60 /
40) P-10 M-7 / N-vinylpyrrolidone copolymer (2
0/80)

P-11 M-7 / diacetone acrylamide copolymer (10/90) P-12 M-10 / sodium methacrylate copolymer (1
5/85) P-13 M-10 / methyl acrylate / methyl methacrylate copolymer (20/40/40) P-14 M-12 / ethyl methacrylate copolymer (33/67) P-15 M-12 / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (15/85) P-16 M-13 / methyl methacrylate copolymer (33/67) P-17 M-13 / 2-acrylamido-2-methyl Sodium propanesulfonate copolymer (20/80) P-18 M-13 / N-acryloylmorpholine copolymer (20/80) P-19 M-13 / methoxypolyethylene glycol (23-mer) monomethacrylate copolymer Combined (50/5
0) P-20 M-18 / N, N-dimethylacrylamide copolymer (5/95)

P-21 M-18 / butyl methacrylate copolymer (30/70) P-22 M-18 / styrene / butyl acrylate copolymer (20/30/50) P-23 M-19 / 2- Acrylamide-2-methylpropanesulfonic acid sodium copolymer (20/80) P-24 M-23 / methyl acrylate copolymer (2
0/80) P-25 M-24 / ethyl acrylate / styrene copolymer (20/50/30) P-26 M-26 / acrylamide copolymer (25 /
75) P-27 M-26 / N, N-dimethylaminoethyl methacrylate copolymer (30/70)

[0024]

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As the polymer hardener used in the present invention,
Preferably, an active olefin polymer hardener, an s-triazine polymer hardener, an active halogen polymer hardener,
An aldehyde-type polymer hardener, a glycidyl-type polymer hardener, and the like are used, more preferably, an active olefin-type polymer hardener is used, and a vinyl sulfone-type polymer hardener is particularly preferable. The layer to which the polymer hardener used in the present invention is added is a photographic constituent layer located farther than the silver halide emulsion layer closest to the support of the photosensitive sheet,
As long as this condition is satisfied, another silver halide emulsion layer may be used, or a protective layer, an ultraviolet absorbing layer, a white reflective layer, a color material layer, an intermediate layer or a color mixing prevention layer may be used. Of these, a layer as far as possible from the support is preferred, and a layer located farthest away is particularly preferred. The layer to which the polymer hardener used in the present invention is added may be divided into two or more layers. The pH of the coating solution for the layer to which the polymer hardener used in the present invention is added is preferably 5.0 to 8.0, and 5.5.
-7.0 is more preferable. The addition amount of the polymer hardener used in the present invention is 1 to 1 of the hydrophilic colloid of the layer to be added.
It is preferably 30% by mass, more preferably 5 to 15% by mass. In the present invention, the above-mentioned polymer hardener and a low-molecular hardener having a number average molecular weight of less than 2,000 may be used in combination.

Next, the color diffusion transfer photosensitive material of the present invention will be described. In a typical form of the color diffusion transfer film unit, the image receiving element and the photosensitive element are laminated on one transparent support, and after the transfer image is completed, there is no need to peel the photosensitive element from the image receiving element. It is a form. More specifically, the image receiving element comprises at least one mordant layer, and 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 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 image-forming compound, magenta The dye image-forming compound and the cyan dye image-forming compound are respectively combined (herein, the term “infrared-sensitive emulsion layer” means 700 nm or more, especially 74 nm).
An emulsion layer having a spectral sensitivity maximum with respect to light of 0 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 image forming compound-containing layer so that the transferred image can be viewed through the transparent support.

A light-shielding layer is provided between the white reflective layer and the photosensitive layer so that the developing process can be completed in a light place. Further, if desired, a release layer may be provided at an appropriate position so that all or a part of the photosensitive element can be separated from the image receiving element. Such an embodiment is disclosed in, for example, Japanese Patent Application Laid-Open No. 56-67.
840 and Canadian Patent 674,082.

A pressure-rupturable container (processing element) further containing an alkaline processing liquid may be combined with the above-described embodiment. In particular, in a peeling-free film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon.

Hereinafter, each component which can be used in the light-sensitive material of the present invention will be described in more detail.

I. Photosensitive sheet and cover sheet A) Support The support for the photosensitive sheet used in the present invention may be any smooth transparent support usually used for photographic photosensitive materials, and examples thereof include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. It is preferably used and provided with an undercoat layer. Preferably, the support usually contains a trace amount of a dye or a pigment such as titanium oxide to prevent light piping. The thickness of the support is 5
It is 0 to 350 μm, preferably 70 to 210 μm, and more preferably 80 to 150 μm. If necessary, a layer for curl balance or an oxygen barrier layer described in JP-A-56-78833 may be provided on the back side of the support.

B) Image Receiving Layer The dye image receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This may be a single layer or a multilayer structure in which mordants having different mordant powers are applied in layers. This is described in JP-A-61-25255.
No. 1. As the mordant, a polymer mordant is preferable. The polymer mordant is a polymer containing secondary and tertiary amino groups, a polymer containing a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation and having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. Things. The coating amount of the mordant is generally 0.5
10 g / m ² , preferably 1.0 to 5.0 g / m ² , particularly preferably ² to 4 g / m ² .

As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone and the like are used, and gelatin is preferred. In the image receiving layer, JP-A-62-30620
No. 62-30621, JP-A-62-215272.
The anti-fading agent described in (1) can be incorporated.

C) White Reflective Layer The white reflective layer forming the white background of a color image usually contains a white pigment and a hydrophilic binder. As white pigments for the white reflective layer, barium sulfate, zinc oxide, barium stearate,
Silver flakes, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, titanium dioxide and the like are used. Further, non-film-forming polymer particles made of styrene or the like are also used. These may be used alone or as a mixture as long as the desired reflectance is obtained. A particularly useful white pigment is titanium dioxide.

The whiteness of the white reflective layer varies depending on the type of the pigment, the mixing ratio of the pigment and the binder, and the amount of the pigment applied, but the light reflectance is desirably 70% or more. In general, as the amount of the pigment applied increases, the whiteness improves.However, when the image forming dye diffuses through this layer, the pigment becomes resistant to the diffusion of the dye. Is desirable. 5 to 40 g of titanium dioxide /
m ² , preferably 10 to 25 g / m ² , and a white reflective layer having a light reflectance of 78 to 85% with light having a wavelength of 540 nm is preferred. Titanium dioxide can be selected from various commercially available brands. Among them, it is particularly preferable to use rutile type titanium dioxide. Many commercial products are
Surface treatment is performed with alumina, silica, zinc oxide, or the like, and a surface treatment amount of 5% or more is desirable in order to obtain high reflectance. Examples of commercially available titanium dioxide include those described in Research Disclosure No. 15162, in addition to DuPont's Ti-pure R931.

As a binder for the white reflective layer, an alkali-permeable polymer matrix such as gelatin, polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose can be used. A particularly desirable binder for the white reflective layer is gelatin. The ratio of white pigment to gelatin is 1/1 to 2
0/1 (mass ratio), preferably 5/1 to 10/1 (mass ratio). In the white reflective layer, JP-B-62-3062
No. 0 or 62-30621 can also be incorporated.

D) Light-shielding layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the white reflective layer and the photosensitive layer. As the light-shielding agent, any material having a light-shielding function is used, and carbon black is preferably used. U.S. Pat.
Degradable dyes described in US Pat. No. 5,966 or the like may be used.
As the binder for coating the light-blocking agent, any binder capable of dispersing carbon black may be used, and gelatin is preferred. As a carbon black raw material, for example, Do
nnel Voet "Carbon Black" MarcelDekker, Inc. (19
Any method such as a channel method, a thermal method, and a furnace method described in 76) can be used. The particle size of the carbon black is not particularly limited, but is preferably 90 to 1800 °. The addition amount of the black pigment as a light-shielding agent may be adjusted according to the sensitivity of the photosensitive material to be shielded from light, but is preferably about 5 to 10 in optical density.

E) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming compound is provided above the light-shielding layer. The components will be described below.

(1) Dye image forming compound Specific examples of the dye image forming compound are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. , 383, 4,195,992, 4,148,641, 4,148,643 and 4,336,322: JP-A-51-114930,
No. 56-71072: Research Disclosure 1763
No. 0 (1978) and No. 16475 (1977).

Examples of magenta dyes: US Pat. No. 3,453,453
No. 107, No. 3,544,545, No. 3,932,3
No. 80, No. 3,931,144, No. 3,932,30
No. 8, 3,954, 476, 4, 233, 237
Nos. 4,255,509 and 4,250,246
Nos. 4,142,891, 4,207,104
No. 4,287,292, JP-A-52-10672.
No. 7, No. 53-23628, No. 55-36804,
No. 56-73057, No. 56-71060, No. 55
-134, JP-A-7-120901 and 8-286
No. 343, No. 8-286344, No. 8-292535
What is described in the issue.

Examples of cyan dyes: US Pat. No. 3,482,9
No. 72, No. 3,929,760, No. 4,013,63
No. 5, 4,268,625, 4,171,220
Nos. 4,242,435 and 4,142,891
Nos. 4,195,994 and 4,147,544
No. 4,148,642; British Patent 1,551,1
No. 38; JP-A-54-99431, JP-A-52-8827.
No. 53-47823, No. 53-143323,
Nos. 54-99431 and 56-71061; European Patents (EP) 53,037 and 53,040;
Research Disclosure 17,630 (1978) and 16,475 (1977).

Dye image forming compounds which form a dye by coupling can also be used. For example, JP-A-8-28634
No. 0, No. 9-152705, Japanese Patent Application No. 8-357190
No., JP-A Nos. 10-186564 and 10-29338.
No. 8, etc. Also, a positive dye image forming compound can be used. In this case, a negative emulsion may be used as the silver halide emulsion. An example of this is disclosed in
No. 6542, No. 4-155332, No. 4-17234
No. 4, No. 4-172450, No. 4-318844,
No. 356046, No. 5-45824, No. 5-458
No. 25, No. 5-53279, No. 5-107710,
5-241302, 5-107708, 5-
No. 232659 and U.S. Pat. No. 5,192,649.

These compounds are disclosed in JP-A-62-2152.
No. 72, pages 144 to 146. These dispersions are described in JP-A-62-2152.
No. 72, pages 137 to 144 may be included. Specific examples of these dye-forming compounds include the following compounds. Dye in the following compounds represents a dye group, a temporarily shortened dye group, or a dye precursor group.

[0043]

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[0044]

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[0045]

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(2) Silver halide emulsion The silver halide emulsion used in the present invention may be a negative emulsion which mainly forms a latent image on the surface of silver halide grains,
An internal latent image type direct positive emulsion which forms a latent image inside silver halide grains may be used.

The internal latent image type direct positive emulsion may be, for example, a so-called “conversion type” emulsion prepared by utilizing the difference in solubility of silver halide, or may be doped with a metal ion.
Or a "core / shell" emulsion in which at least the photosensitive sites of the silver halide inner nucleus (core) grains subjected to chemical sensitization or both are coated with an outer shell of silver halide. These are described in U.S. Pat. Nos. 2,592,250 and 3,206,313, British Patent 1,027,146, and U.S. Pat.
Nos. 6, 3,935,014 and 3,447,927
No. 2,297,875, No. 2,563,785
Nos. 3,551,662 and 4,395,478
No. 2,728,108, US Patent 4,43.
1,730 and the like.

When an internal latent image type direct positive emulsion is used, it is necessary to give a surface fog nucleus using light or a nucleating agent after image exposure. As a nucleating agent for that,
U.S. Pat. Nos. 2,563,785 and 2,588,982
Hydrazines described in US Pat. No. 3,227,5
No. 52, hydrazines and hydrazones described in British Patent No. 1,283,835, JP-A-52-69613.
No. 3,615,615 and 3,719,4
Nos. 94, 3,734, 738 and 4,094,68
Heterocycle 4 described in No. 3, No. 4, 115, 122, etc.
Grade salt compounds, sensitizing dyes having a nucleating substituent described in US Pat. No. 3,718,470 in dye molecules, US Pat. Nos. 4,030,925 and 4,031,1
No. 27, No. 4, 245, 037, No. 4, 255, 51
No. 1, 4,266,013, 4,276,364
Thiourea-linked acylhydrazine-based compounds described in US Pat. No. 2,012,443 and the like, and US Pat. Nos. 4,080,270 and 4,278,748, British Patent 2,011,391B and the like An acylhydrazine-based compound in which a heterocyclic group such as a thioamide ring or a triazole or a tetrazole described in (1) is bonded as an adsorptive group is used.

In the present invention, spectral sensitizing dyes can be used in combination with these negative emulsions and internal latent image type direct positive emulsions. For a specific example thereof, see JP-A-59-18.
Nos. 0550 and 60-140335, Research Disclosure (RD) 17029, U.S. Pat.
No. 6,300, No. 2,078,233, No. 2,08
9,129, 2,165,338, 2,23
No. 1,658, No. 2,917,516, No. 3,35
No. 2,857, No. 3,411,916, No. 2,29
5,276, 2,481,698, 2,68
8,545, 2,921,067, 3,28
2,933, 3,397,060, 3,66
No. 103, No. 3,335,010, No. 3,35
2,680, 3,384,486, 3,62
No. 3,881, No. 3,718,470, No. 4,02
5,349 and the like.

(3) Composition of photosensitive layer To reproduce a natural color by the subtractive color method, the above-mentioned dye which provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the above-mentioned spectral sensitizing dye A photosensitive layer comprising at least two of the combinations with the image forming compound is used. In the present invention, "the combination of the dye-forming compound and the silver halide emulsion layer" means that the dye-forming compound is coated so that the dye can be formed by a development reaction of the silver halide emulsion. More specifically, the emulsion and the dye image-forming compound may be applied in a superposed manner as separate layers, or may be mixed and applied as a single layer. When the dye-forming compound has an absorption in the spectral sensitivity range of the emulsion combined with the coated dye-forming compound, a separate layer is preferred. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities,
An optional layer may be provided between the emulsion layer and the dye image forming compound layer. For example, a layer containing a nucleation development accelerator described in JP-A-60-173541, JP-B-60-152.
The color image density can be increased by providing a partition layer described in No. 67, and the sensitivity of the photosensitive element can be increased by providing a reflective layer.

The reflection layer is a layer containing a white pigment and a hydrophilic binder. Preferably, the white pigment is titanium oxide and the hydrophilic binder is gelatin. The coating amount of titanium oxide is 0.1 g / m ^{2 to} 8 g / m ² , preferably 0.1 g / m ² .
It is a ^{2g / m 2 ~4g / m 2} . Examples of the reflective layer are described in JP-A-60-91354.

In a preferred multilayer structure, a combination unit of a blue-sensitive emulsion, a combination unit of a green-sensitive emulsion, and a combination unit of a red-sensitive emulsion are sequentially arranged from the exposure side. Arbitrary layers can be provided between the emulsion layer units as needed. In particular, it is preferable to provide an intermediate layer in order to prevent an unfavorable effect of the development effect of one emulsion layer on other emulsion layer units. In the present invention, an irradiation prevention layer, a UV absorber layer, a protective layer, and the like are provided as necessary.

F) Peeling Layer In the present invention, a peeling layer can be provided, if necessary, to peel off the photosensitive sheet in the unit at an arbitrary place after processing. Therefore, this release layer must be easily peelable after the treatment.

As a material for this purpose, for example, Japanese Unexamined Patent Publication No.
Nos. 7-8237, 59-220727 and 59-2
No. 29555, No. 49-4653, U.S. Pat.
20,835 and 4,359,518,
No.-4334, No.56-65133, No.45-240
No. 75, U.S. Pat. Nos. 3,227,550 and 2,75
9,825, 4,401,746, 4,36
No. 6,227 or the like can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. Examples include hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. Other examples include various natural polymers such as alginic acid, pectin, gum arabic, and the like. Various modified gelatins such as acetylated gelatin and phthalated gelatin can also be used. Further, another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethyl methacrylate, polybutyl methacrylate, or a copolymer thereof, or the like. The release layer may be a single layer or, for example, disclosed in JP-A-59-220727 and JP-A-60-60642.
It may be composed of a plurality of layers as described in the number.

The pH of the film surface of the light-sensitive sheet before development on the emulsion layer side is generally selected to be near neutral, but the effect of reducing the density of the white background in the light-sensitive material of the present invention is effectively exhibited. 4.5 to 7.0, preferably 5.0
-6.5 is particularly preferred. The pH of the film surface is adjusted by adding an acid or an alkali to each constituent layer of the photosensitive sheet. Preferred examples of the acid include hydrochloric acid, sulfuric acid, and citric acid, and examples of the preferably used alkali include sodium hydroxide and potassium hydroxide. The pH of the film surface can be measured by spotting a small amount of distilled water on the film surface of the photosensitive sheet and then closely contacting a flat glass pH electrode.

The color diffusion transfer photosensitive material of the present invention preferably has a neutralizing function between the support and the photosensitive layer, between the support and the image receiving layer, or on the cover sheet.

G) Support The support for the cover sheet used in the present invention may be any smooth transparent support commonly used for photographic light-sensitive materials, and examples thereof include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. ,
It is preferable to provide an undercoat layer. The support preferably contains a trace amount of a dye to prevent light piping.

H) Layer Having Neutralizing Function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize the alkali introduced from the treatment composition. Accordingly, a multilayer structure including layers such as a neutralization rate control layer (timing layer) and an adhesion strengthening layer may be used. Preferred acidic substances are those containing an acidic group having a pKa of 9 or less (or a precursor group that provides such an acidic group by hydrolysis), and more preferably oleic acid described in US Pat. No. 2,983,606. Higher fatty acids such as US Pat. No. 3,362,819
Of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in US Pat. Ester copolymers;
No. 4,139,383 and Research Disclosure No. 16102 (19
And latex-type acidic polymers as disclosed in (77). In addition, U.S. Pat.
8,493, JP-A-52-153739, and JP-A-53-153739.
No. 1023, No. 53-4540, No. 53-4541
And the acidic substances disclosed in JP-A-53-4542 and the like.

Specific examples of the acidic polymer include ethylene,
Copolymers of vinyl monomers such as vinyl acetate and vinyl methyl ether with maleic anhydride and their n-butyl esters, copolymers of butyl acrylate and acrylic acid, cellulose, acetate hydrogendiene phthalate and the like.

The above-mentioned polymer acids can be used in a mixture with a hydrophilic polymer. Such polymers include:
Examples include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and polymethylvinylether. Among them, polyvinyl alcohol is preferred. Further, a polymer other than the hydrophilic polymer in the polymer acid,
For example, cellulose acetate or the like may be mixed.

The amount of the polymer acid applied is controlled by the amount of alkali developed on the photosensitive element. The equivalent ratio of the polymer acid to the alkali per unit area is preferably from 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stain is generated on a white background portion. If the amount is too large, inconveniences such as a change in hue and a decrease in light resistance are caused. A more preferred equivalent ratio is 1.0 to 1.3. If the amount of the hydrophilic polymer to be mixed is too large or too small, the quality of the photograph is deteriorated. The mass ratio of the hydrophilic polymer to the polymer acid is 0.1 to 10, preferably 0.3 to 10.
３3.0.

In the layer having a neutralizing function used in the present invention, additives can be incorporated for various purposes. For example, hardeners known to those skilled in the art to harden this layer,
In order to improve the brittleness of the film, a polyhydric hydroxyl compound such as polyethylene glycol, polypropylene glycol and glycerin can be added. In addition, if necessary, an antioxidant, a fluorescent whitening agent, a development inhibitor and a precursor thereof may be added.

The timing layer used in combination with the neutralizing layer has a low alkali permeability such as, for example, gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like. Polymers made by copolymerizing small amounts of hydrophilic comonomers such as acrylic acid monomers,
Latex polymers that increase the activation energy of alkali permeation; polymers having a lactone ring are useful.

Among them, Japanese Patent Application Laid-Open No. 54-136328,
U.S. Pat. Nos. 4,267,262 and 4,009,030
No. 4,029,849 and the like, a timing layer using cellulose acetate;
No. 335, No. 56-69629, No. 57-6843
No. 4,056,394 and 4,061,4
Nos. 96, 4,199,362, 4,250,24
No. 3, 4,256, 827, 4,268,604
A latex polymer prepared by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid; a polymer having a lactone ring disclosed in U.S. Pat. No. 4,229,516; -25735
Nos. 56-97346 and 57-6842, European Patent (EP) 31,957A1, 37,72
The polymers disclosed in Nos. 4A1, 48,412 A1, and the like are particularly useful.

In addition, those described in the following documents can also be used. U.S. Pat. Nos. 3,421,893 and 3,455
686, 3,575,701, 3,778,2
No. 65, No. 3,785,815, No. 3,847,61
No. 5, 4,088, 493, 4, 123, 275
No. 4,148,653, 4,201,587
No. 4,288,523 and 4,297,431
No., West German Patent Application (OLS) 1,622,936, 2,162,277, Research Disclosure 1516
2, No. 151 (1976). The timing layer using these materials can be used as a single layer or as a combination of two or more layers.

In the timing layer made of these materials, for example, US Pat. No. 4,009,029, West German Patent Application (OLS) 2,913,164, and 3,014,6
No. 72, JP-A Nos. 54-155837 and 55-138.
No. 745, and the like, and a development inhibitor and / or a precursor thereof disclosed in US Pat.
Hydroquinone precursor disclosed in No. 78,
It is also possible to incorporate other useful photographic additives or precursors thereof. Further, as a layer having a neutralization function, JP-A-63-168648 and JP-A-63-168648
Providing an auxiliary neutralizing layer as described in JP-B-168649 is effective in that a change in transfer density with time after processing is reduced.

I) Others In addition to the layer having a neutralizing function, a layer having an auxiliary function may have a back layer, a protective layer, a filter dye layer and the like. The back layer is provided for adjusting curl and imparting slipperiness. Filter dyes may be added to this layer. The protective layer is mainly used for preventing adhesion to the back surface of the cover sheet and adhesion to the protective layer of the photosensitive material when the photosensitive material and the cover sheet are overlapped. The sensitivity of the photosensitive layer can be adjusted by adding a dye to the cover sheet. The filter dye is directly in the support of the cover sheet or a layer having a neutralizing function, and further the back layer,
You may add to a protective layer, a capture mordant layer, etc., and may provide a single layer.

II. Alkali processing composition The processing composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element, and is disposed on the back of the support or on the side opposite to the processing solution of the photosensitive layer to form a pair with the light shielding layer. Thus, the photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the contained components. For this purpose, the composition contains an alkali, a thickener, a light-blocking agent, a developer, and further, a development accelerator for controlling the development, a development inhibitor, and an antioxidant for preventing the deterioration of the developer. Etc. A light-shielding agent is always contained in the composition for light-shielding.

The alkali is sufficient to adjust the pH of the solution to 12 to 14, and includes a hydroxide of an alkali metal (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide),
Examples thereof include alkali metal phosphates (eg, potassium phosphate), guanidines, and quaternary amine hydroxides (eg, tetramethylammonium hydroxide). Of these, potassium hydroxide and sodium hydroxide are preferable.

The thickener is used in order to spread the treatment liquid uniformly.
Also, it is necessary to maintain the close contact between the photosensitive layer and the cover sheet. For example, alkali metal salts of polyvinyl alcohol, hydroxyethyl cellulose, and carboxymethyl cellulose are used, and preferably, hydroxyethyl cellulose and sodium carboxymethyl cellulose are used. As the light-shielding agent, any dye or pigment can be used as long as the light-shielding agent does not diffuse to the dye image-receiving layer to produce stain, or a combination thereof. A typical example is carbon black.

As the preferred developing agent, any one can be used as long as it cross-oxidizes the dye image-forming substance and does not substantially generate stain when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor form. These developing agents may be contained in an appropriate layer of the photosensitive sheet or in an alkaline processing solution. Specific examples of the compound include aminophenols and pyrazolidinones, and among them, pyrazolidinones are particularly preferable because they generate less stain. For example, 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3'-methyl-phenyl) -4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, and the like.

Either a photosensitive sheet, a cover sheet or an alkali treatment composition, a development accelerator described in JP-A-62-215272, pages 72 to 91, a hardener described on pages 146 to 155, a hardener described in pages 201 to 210 Surfactant, 210
Fluorine-containing compounds described on pages 223 to 222, thickeners described on pages 225 to 227, antistatic agents described on pages 227 to 230, 23
It may contain a polymer latex described on pages 0 to 239, a matting agent described on page 240, and the like. Also, Japanese Patent Laid-Open No. 6-2
73907, JP-A-7-134386, JP-A-7-134386
No. 175193 and JP-A-7-287372.
A graded amine latex can be included.

Further, these alkali liquid compositions have a developed thickness (amount of the processing liquid per m ² after transferring the processing liquid) of 20 μm to ² μm.
It is desirable that the image is spread on the photosensitive element at a thickness of 00 μm. The processing temperature when processing a photosensitive material is preferably from 0 to 50 ° C, more preferably from 0 to 40 ° C.

The light-sensitive material of the present invention has not only a function as a photographing material but also a function as a viewing material. Writing an image on a photosensitive material can be performed not only by photographing using a camera, but also by directly exposing image information (analog information and digital information) to the photosensitive material using various light sources. The obtained image can be used and viewed as various information media other than a so-called photograph. The image of the light-sensitive material of the present invention can be obtained in a short time by developing it in an apparatus after writing the image, and has characteristics particularly suitable for the above applications. The light source for writing the image may be any light source that can modulate the light emission intensity, the light emission time and the like according to the image information. For example, a CRT, LED, LED array, VFPH, organic EL, or the like can be used.
When a color image is written in three colors of B, G, and R, the light source may be combined with a filter and exposed three times.
Exposure can also be performed using three independent light sources B, G, and R. The light-sensitive material of the present invention can be used as a material for a printer as a use other than a photographic material. For example, JP-A-11-344772, Japanese Patent Application 2000-6753
2, 2000-67535, JP-A-11-35259
The photosensitive material of the present invention is preferably used as a material for a portable printer described in No. 5, etc. When used as the above-mentioned material, there are applications where confidentiality of authentication information and tampering prevention are required. There are various methods for imparting the above performance, and a method of printing a security pattern on an image receiving material is preferably used. As this method, for example, US Pat.
0 and 2000-147060 can be preferably used for the photosensitive material of the present invention.

[0075]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 First, a method for preparing a silver halide emulsion will be described. The following eight kinds of silver halide emulsion grains (emulsion-A to emulsion-F) and emulsion-T,
U was prepared.

Preparation of Emulsion-A (octahedral internal latent image type direct positive emulsion): 0.05 M potassium bromide, 1 g 3,6-dithia-1,8-octanediol, 0.034 mg lead acetate
And deionized gelatin 60 having a Ca content of 100 ppm or less
g in 1000 ml of an aqueous gelatin solution containing
While maintaining the temperature at 5 ° C., a 0.4 M aqueous solution of silver nitrate and a 0.4 M aqueous solution of potassium bromide were controlled by the double jet method while controlling the addition rate of the aqueous solution of potassium bromide so that the pBr was 1.60. Was added over 40 minutes. When the addition was completed, octahedral silver bromide crystals (hereinafter referred to as core particles) having an average particle size (equivalent sphere size) of about 0.7 μm and a uniform particle size were produced.

Next, core chemical sensitization was performed under the following conditions. 1. Tank: hemispherical bottom shape with a metal surface coated with Teflon (registered trademark) with a thickness of 120 µm by a fluororesin material FEP developed by Du Pont 2. Stirrer blade: Seamless propeller type with a Teflon-coated metal surface.

Sodium thiosulfate 1
mg, potassium tetrachloroaurate 90 mg and potassium bromide 1.
3 g of an aqueous solution of 2 g dissolved in 1000 ml of water is added,
Chemical sensitization treatment was performed by heating at 80 ° C. for 80 minutes. 0.1% was added to the emulsion solution thus chemically sensitized.
After the addition of 5 M potassium bromide, a 0.9 M aqueous solution of silver nitrate and a 0.9 M aqueous solution of potassium bromide are added to the aqueous solution of 0.9 M potassium bromide in a controlled double jet method while maintaining the temperature at 75 ° C., as in the preparation of the core particles. The silver nitrate aqueous solution 6
70 ml was added over 70 minutes. The emulsion was washed with water by a conventional flocculation method, and the above-mentioned gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added to make the average particle size (equivalent sphere size) about 1.2 μm. Octahedral silver bromide crystals (hereinafter referred to as internal latent image type core / shell grains) were obtained.

Next, 100 mg of sodium thiosulfate and 40 mg of sodium tetraborate were added to the internal latent image type core / shell emulsion.
Was added to 1000 ml of water and 3 ml of an aqueous solution was added.
After addition of mg of poly (N-vinylpyrrolidone) and aging at 60 ° C., 0.005 M potassium bromide was added to prepare an octahedral internal latent image type direct positive emulsion.

Preparation of emulsions BF (octahedral internal latent image type direct positive emulsion): In the preparation method of emulsion-A, the addition time of silver nitrate aqueous solution and potassium bromide aqueous solution was changed, and the amount of added chemicals was further changed. Was carried out to obtain an octahedral internal latent image type direct positive silver halide emulsion having an average particle size (equivalent sphere diameter) shown in Table 1 having a uniform particle size.

[0082]

[Table 1]

Preparation of Emulsion-T (hexagonal plate-like internal latent image type direct positive emulsion): In 1.2 liter of an aqueous gelatin solution containing 0.05 M of potassium bromide and 0.7% by mass of gelatin having an average molecular weight of 100,000 or less. And 1.4 containing the aforementioned gelatin.
33 ml of each of the M aqueous silver nitrate solution and the 2 M aqueous potassium bromide solution were simultaneously mixed for 1 minute by the double jet method with vigorous stirring. During this time, the gelatin aqueous solution was kept at 30 ° C. Further, 300 ml of a gelatin solution containing 10% by mass of deionized gelatin having a Ca content of 100 ppm or less was added, and the temperature was raised to 75 ° C. Next, 40 ml of 0.9 M silver nitrate aqueous solution
Was added over 3 minutes, a 25% by mass aqueous ammonia solution was added, and aging was performed at 75 ° C. After the ripening, ammonia was neutralized, and then 5 mg of lead acetate (added as an aqueous solution) was added, and an accelerated flow rate of 1 M silver nitrate aqueous solution and 1 M potassium bromide aqueous solution while maintaining pBr at 2.5 (at the end of the aging) (The flow rate was 6 times the flow rate at the start) and added by the double jet method (the amount of the used silver nitrate aqueous solution was 500 ml).

The particles thus formed (hereinafter referred to as core particles) were washed with water by a conventional flocculation method, and gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added thereto, and 750 g of a hexagonal flat plate was added. Core particles were obtained. The obtained hexagonal flat core particles have an average projected area circle equivalent diameter of 0.9 μm and an average thickness of 0.20.
μm, and 95% of the total projected area was occupied by hexagonal tabular grains.

Next, core chemical sensitization was performed under the following conditions. 1. Tank: hemispherical bottom with metal surface coated with Teflon by fluoropolymer FEP developed by Du Pont with a thickness of 120 μm. 2. Stirrer blade: Seamless propeller type with a Teflon-coated metal surface.

The hexagonal tabular core emulsion 200 g was added to water 13
00ml, potassium bromide 0.11M and deionized gelatin 4
After adding 0 g and raising the temperature to 75 ° C, 3,6-dithia-
2.4 g of an aqueous solution obtained by dissolving 0.3 g of 1,8-octanediol, 10 mg of sodium benzenethiosulfate, 90 mg of potassium tetrachloroaurate and 1.2 g of potassium bromide in 1000 ml of water, and 15 mg of lead acetate (added as an aqueous solution) And heated at 75 ° C. for 180 minutes to perform a chemical sensitization treatment. In the same manner as in the preparation of the core particles, the chemically sensitized core particles were mixed with a 2M aqueous solution of silver nitrate.
The double jet method was carried out at an accelerated flow rate (the flow rate at the end was 3 times the flow rate at the start) while adjusting the addition rate of the aqueous solution of potassium bromide to adjust the pBr to 2.2. (The amount of the used aqueous silver nitrate solution was 810 ml).

After adding 0.3 M potassium bromide, the emulsion was washed with water by a conventional flocculation method, and gelatin was added. Thus, a hexagonal tabular internal latent image type core / shell emulsion was obtained. The obtained hexagonal tabular grains have an average projected area equivalent circle diameter of 2.0 μm, an average thickness of 0.38 μm, an average volume size of 1.3 (μm) ³ and 88% of the total projected area are hexagonal tabular grains. Occupied by particles. Next, 100 mg of sodium thiosulfate and 4 parts of sodium tetraborate were added to the hexagonal tabular internal latent image type core / shell emulsion.
15 mg of an aqueous solution in which 0 mg was dissolved in 1000 ml of water was added, and 20 mg of poly (N-vinylpyrrolidone) was further added.
By heating at 100 ° C. for 100 minutes, the grain surface was chemically sensitized to prepare a hexagonal tabular internal latent image type direct positive emulsion.

Preparation of Emulsion-U (hexagonal tabular internal latent image type direct positive emulsion): At the time of forming the outer shell of Emulsion-T, 0.15 mol% of iodine was uniformly contained, and the outer shell forming amount was further reduced. By increasing, the average projected area circle equivalent diameter becomes 2.5
μm, the average grain thickness was 0.45 μm, the average volume size was 1.7 (μm) ³ , and 88% of the total projected area was occupied by hexagonal tabular grains. Next, AgI corresponding to 0.04 mol% of the silver amount required for grain formation at the start of shell chemical sensitization of the hexagonal tabular internal latent image type core / shell emulsion was used.
After adding the fine grain emulsion-X, the same shell chemical sensitization as in the emulsion-T was performed to prepare a hexagonal tabular internal latent image type direct positive emulsion.

Preparation of Emulsion-X (AgI fine grain emulsion) 0.5 g of potassium iodide and 26 g of gelatin were added to water, and 80 ml of an aqueous silver nitrate solution containing 40 g of silver nitrate and 39 g of iodine were stirred into a solution kept at 35 ° C. 80 cc of an aqueous solution containing potassium iodide was added over 5 minutes. At this time, the addition flow rates of the silver nitrate aqueous solution and the potassium iodide aqueous solution were each 8 ml / min at the start of the addition, and the addition flow rates were linearly accelerated so that the addition of 80 ml was completed in 5 minutes. After the formation of the particles was completed, the soluble salts were removed by settling at 35 ° C. Next, the temperature was raised to 40 ° C., and 10.5 g of gelatin and 2.56 g of phenoxyethanol were added, and the pH was adjusted to 6.8 with sodium hydroxide. The obtained emulsion had a finished amount of 73.
Monodispersed AgI fine particles having an average diameter of 0.015 μm were obtained at 0 g.

Using the emulsions A to F, T, and U as described below, a comparative photosensitive element 10 having the structure shown in Tables 2 to 6 below:
1 was created. At the end of the shell chemical sensitization, the sensitizing dye was added at the dye type, dispersion form, addition temperature and amount shown in Table 7 below.

[0091]

[Table 2]

[0092]

[Table 3]

[0093]

[Table 4]

[0094]

[Table 5]

[0095]

[Table 6]

[0096]

[Table 7]

[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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Preparation of Cover Sheet A cover sheet was prepared by applying a layered composition as shown in Table 8 on a transparent support having a thickness of 75 μm.

[0111]

[Table 8]

The chemical structural formulas and the like of the compounds used in the cover sheet are shown below.

[0113]

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[0114]

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The formulation of the alkali treatment composition is shown below. (Per kg of finished product) Silver nitrate 0.09 g Carbon black (Mitsubishi Chemical Corporation, trade name: Carbon Black MA220) 147 g Additive (22) 7.90 g Carboxymethylcellulose Na salt 56.0 g Benzyl alcohol 2.41 g Additive ( 23) 2.10 g potassium sulfite (anhydrous) 1.90 g 5-methylbenzotriazole 2.25 g 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 3.78 g 1-phenyl-4-hydroxymethyl -4-methyl-3-pyrazolidone 16.0 g potassium hydroxide 50.2 g aluminum nitrate 0.60 g zinc nitrate 0.60 g additive (24) 2.76 g additive (14) 0.18 g 1,2-benz Isothiazolin-3-one 0.003 g

[0116]

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For the photosensitive element 101, the exemplified compound or the comparative compound (the hardeners (1) and (2))
As shown in Table 9, except that they were further added to and coated on the photographic constituent layers to produce photosensitive elements 102 to 113. In the table below, the term "sample" refers to a photosensitive material sample comprising these photosensitive elements, the cover sheet, and the alkali treatment composition.

[0118]

[Table 9]

Next, the photosensitive elements 101 to 113 were exposed to white light from the emulsion layer side, and then superposed on the cover sheet. The alkali treatment composition was placed between the two materials at a temperature of 5 ° C. to a thickness of 45 μm. Was developed using a pressure roller. After leaving still at 5 ° C. for 3 minutes, xenon light of 70,000 lux was irradiated from the cover sheet side for 1 minute. Observing the obtained white image, spots (20 to 100 μm in diameter) generated by light leakage at the time of xenon light irradiation are observed.
m black spots). Next, the same treatment and test as described above were performed at a temperature of 25 ° C. In order to examine the photographic performance of the light-sensitive material, the light-sensitive elements 101 to 113 were exposed from the emulsion layer side through a continuous gray wedge, then overlapped with the cover sheet, and the alkali processing composition was pressed between the two materials. It was developed as above using a roller. After the treatment at 25 ° C. for 2 hours, the transfer density was measured with a color densitometer, and the maximum color density of each of yellow, magenta and cyan was determined. Table 10 shows the results.

[0120]

[Table 10]

In Table 10, the sample 101 (comparative example) has no spots at a temperature of 25 ° C., but has many black spots at 5 ° C. On the other hand, sample 102
-104 (invention), the polymer hardener (P
By adding -2), spots at a temperature of 5 ° C are significantly reduced. As in Samples 105 and 106 (the present invention), a polymer hardener (P-
It can be seen that spots could be suppressed by adding 2), but spots could not be suppressed when added to a layer close to the support as in Sample 107 (Comparative Example). As shown in Samples 108 to 111 (Comparative Examples), when a low molecular weight hardener was used, not only the spots could not be suppressed, but also the color density decreased. P-2 (samples 103 to 1) was used as a polymer hardener.
07), a vinyl sulfone-type polymer hardening agent is preferred, but a compound containing an active halogen such as P-8 (sample 112) or an aldehyde type such as P-13 (sample 113) It can also be seen that this is also effective in preventing spots.

[0122]

The color diffusion transfer photographic light-sensitive material of the present invention is excellent in that a spot-like image defect does not occur and a good image can be obtained even when exposed to strong light after processing at a low temperature. It works.

Claims (3)

[Claims] 1. A color diffusion transfer photographic light-sensitive material which forms an image by developing an alkaline processing composition between a light-sensitive sheet having at least one silver halide emulsion layer on a support and a transparent cover sheet. A color diffusion transfer photographic light-sensitive material comprising a polymer hardener in at least one of the photographic constituent layers located farther than the silver halide emulsion layer closest to the support in the light-sensitive sheet. . 2. The method according to claim 1, wherein a polymer hardener is contained in a photographic constituent layer farthest from the support, on the side of the silver halide emulsion layer with respect to the support in the photosensitive sheet. Color diffusion transfer photographic photosensitive material. 3. The color diffusion transfer photographic light-sensitive material according to claim 1, wherein the polymer hardener is a polymer hardener having a vinyl sulfone structure.