JPH0235451A - Color photosensitive material - Google Patents

Abstract

PURPOSE:To improve the raw shelf-life of the title material, using a compd. capable of supplying a dye capable of being reduced, by incorporating a specified reducer in the title material. CONSTITUTION:The color photosensitive material is composed of a thermodevelopable color photosensitive material contg. a photosensitive silver halide, a binder, the compd. capable of supplying the pigment capable of being reduced, and the reducer. In the formula, R<1> and R<2> are hydrogen or halogen atom, etc., R<3> is alkylene group substd. with alkyl group, R<4>-R<8> are each hydrogen or halogen atom, etc., X is CO or SO2 group, (m) and (n) are each 0 or 1. The concrete example of the reducing agent is exemplified by a compd. shown by formula II, etc. The reducer together with an electron transfer (precursor) may be incorporated in the photosensitive material to promote an electron transfer between the reducer and a developable silver halide.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a color photosensitive material, and in particular to a color photosensitive material that can provide a positive color image with high density and good color reproducibility, and has a long shelf life. This paper relates to excellent color photosensitive materials.

(Prior Art and its Problems) Many methods have been proposed for obtaining positive color images by diffusion transfer.

For example, U.S. Patent Hirojjri λri No. 0, ≠, 3j6, 2
Hirori issue, same≠,,3! r, j21, JP-A-1983-
31! JJ issue, same zz-iior core issue, same j! -73
0F27, 14-/14LJ4c2, sameyotar/
Yo 1 → j issue, same 6 koko l! In Core Q etc., an oxidized dye-donating compound without dye-releasing ability is made to coexist with a reducing agent or its precursor, and the reducing agent is added to the silver dihalide according to the amount of light applied by wet development or thermal development. A method has been proposed in which a diffusible dye is released by oxidizing the dye and reducing it using the reducing agent that remains unoxidized. In addition, European Patent Publication No. 0F Hiro No. 117-AI2F (Vol.
No. 2.2) contains compounds that release diffusible dyes by a similar mechanism, such as those that release diffusible dyes by reductive cleavage of the N-X bond (X represents an oxygen atom, nitrogen atom, or sulfur atom). Color photosensitive materials have been described that use non-diffusible compounds that emit .

However, when the above-mentioned reducible dye-providing compound is used in combination with a silver halide emulsion together with a reducing agent or its precursor, there are problems in that color images have high staining and storage stability is poor. I understand.

In order to suppress staining in a photothermographic material for positive image formation using such a reducible dye-donating compound, a diffusible electron transfer agent is used in addition to a diffusion-resistant electron donor as a reducing agent. However, the generated electron transfer agent radicals diffuse into other layers with different color sensitivities and cross-oxidize the electron donors there, causing a decrease in image density and impairing color reproduction. becomes worse. For this reason, attempts have been made to provide an intermediate layer between photosensitive layers having different color sensitivities, or to contain a reducing substance in this intermediate layer. Since there are restrictions on the amount of binder and the amount of reducing substance added to each layer in terms of image forming speed, resolution, film quality, etc., further improvements are desired.

(Objective of the Invention) The first object of the present invention is to improve the shelf life of a color light-sensitive material using a reducible dye-providing compound. The first purpose is to increase the image density of the light-sensitive material and improve the color reproducibility.

(Structure of the Invention) An object of the present invention is to provide a heat-developable color photosensitive material having at least a photosensitive silver halide, a binder, a reducible dye-providing compound, and a reducing agent on a support, in which the reducing agent has the following general formula ( Thermal developing power characterized by I) 2 - Achieved by a photosensitive material.

General formula (I) In the formula, R1 and R2 are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an aryl group, an acylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or an acyl group. group, sulfonyl group, carbamoyl group, t or sulfamoyl group, and R
and R may jointly form a carbon ring. R represents an unsubstituted or alkyl group-substituted fullkylene group. R4R5
, R6, R7, R8 are hydrogen atoms, halogen atoms, cyan groups, nitro groups, substituted or unsubstituted alkyl groups, acylamino groups, sulfonamide groups, alkoxy groups,
Aryloxy group, alkylthio group, arylthio group, amino group, acyl group, acyloxy group, carbamoyl group, carbamoylamino group, sulfamoyl group, sulfamoylamino group, alkoxycarbonyl group, aryloxycarbonyl i, wx ring group, alkoxy Sulfonyl group represents an aryloxysulfonyl group R4R5, R6
may be a hydroxyl group. Further, adjacent λ may jointly form a carbocycle or a heterocycle.

X represents -CO- or -SO□-, and m and n each independently represent O or /.

The total number of carbon atoms of R1 to R8 is r or more.

The present invention will be explained in further detail.

In the general formula (I), R1 and R2 are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom), substituted or unsubstituted alkyl groups (carbon number/-400 e.g. methyl, t- butyl, t-octyl, cyclohexyl, n-hexadecyl, 3-decanoamidopropyl),
71J-yl group (carbon number 6-60゜e.g. phenyl, p-
tolyl), azilabano group (2 to to to carbon atoms, e.g. acetyl aba), n-butanamide, co-hexyldecanamide, co(2', μ'-di-t-amylphenoxy)butanamide, be/silylamino), Alkoxy group (carbon number/-400, e.g. methoxy, ethoxy, butoxy, n-octyloxy, methoxyethoxy), aryloxy group (carbon number 6-60, e.g. phenoxy, e-4-
octylphenoxy), alkylthio group (carbon number/-6
0゜For example, butylthio, hexadecylthio), arylthio group (carbon number 6 to t00, e.g. phenylthio, ≠-dodecyloxyphenylthio), acyl group (carbon number 600, e.g. acetyl group, benzoyl group, lauroyl group, etc.), sulfonyl group (7 to 600 carbon atoms, e.g. ebameth/sulfonyl, octane sulfonyl, benzenesulfonyl, dodecyl penze/sulfonyl), carbamoyl group (
Carbon number/-60° e.g. N, N-dioctylcarbamoyl), sulfamoyl group (carbon number 0-+0. e.g. t-
butylsulfamoyl), and R1 and R2 may jointly form a carbocyclic ring.

R3 represents an unsubstituted or alkyl group-substituted fullkylene group (having 7 or more carbon atoms! For example, a methylene group, an ethylene group, a l-methylethylene group, etc.).

R%R, R, R, R are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom),
Cyano group, nitro group, each substituted or unsubstituted alkyl group (carbon number/~to, e.g. cyclohexyl, dodecyl, octadecyl, 3-(N,N-dihexyl-rubamoyl)propyl), acryl amino group (carbon number λ~ Otsu O
0゛For example, octanoylamino, λ-hexyldecanoylamino, pencilylamide), nicotinamide), sulfonamide group (carbon number/~100, for example, hexadecanesulfonamide, dodecyloxybenzenesulfonamide)
, alkoxy group (carbon number 1 to 600, e.g. methoxy, n
-butoxy, hexadecyloxy, comethoxyethoxy), aryloxy groups (carbon atoms 6 to 600, e.g. phenoxy, Hiro-1-octylphenoxy), alkylthio groups (
carbon a/~tO0 e.g. methylthio), arylthio group (carbon number A-400 e.g. phenylthio), amino group (
Carbon number o-ao0 e.g. -NH2, N, N-diethylamino, N, N-dioctadecylamino), acyl group (carbon number 2-600 e.g. acetyl, benzoyl, lauroyl), acyloxy group (carbon number 2-to0 Example j (acetyloxy, benzoyloxy, lauroyloxy), carbamoyl group (number of carbon atoms/~60ol, N-dicyclohexylcarbamoyl, N,N-dioctylcarbamoyl), carbamoylamino group (number of carbon atoms/~600
For example, N'-dodecylcarbamoylamine), sulfamoyl group (carbon number θ to to, e.g. N,N-dibutylsulfamoyl), sulfamoylamino group (carbon number Q-
60° e.g. N', N'-dipropylsulfamoylamino), alkoxycarbonyl group (2 to 0 carbon atoms, e.g. methoxycarbonyl, butoxycarbonyl group), aryloxycarbonyl group (7 to 0 carbon atoms, e.g. phenoxycarbonyl), Heterocyclic groups (j-6 members may have a condensed ring; carbon numbers 1 to 0, e.g., octadecylsuccinimide, furyl, pyridyl), aryloxycarbonyloxy groups (carbon numbers 7 to AQ, e.g., phenoxy carbonyloxy), alkoxysulfonyl group (carbon number/~t0° e.g. methoxysulfonyl, ethoxysulfonyl), alkoxysulfonyl group < carbon aa~60
0 e.g. phenoxysulfonyl) t-represented. R',
R', R' may also be a hydroxy group. Further, adjacent λ may jointly form a carbocycle or a heterocycle.

X represents -CO- or -802-, and m and n each independently represent O or/.

The total number of carbon atoms in R-H is 1 or more.

The compound of general formula (I) may form a bis-form, a tris-form, a polymer, or the like.

Preferred substituents for R1 and R2 in general formula (I) are hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, alkoxy groups, and alkylthio groups, respectively.
Among these, hydrogen atoms, halogen atoms, and substituted or unsubstituted alkyl groups are more preferred, and substituted or unsubstituted alkyl groups are most preferred.

In general formula (I), R preferably has 3 or less carbon atoms.

Preferred substituents for R, R1R, and R R8 in general formula (I) are a hydrogen atom, a substituted or unsubstituted alkyl group, an acylamino group, a sulfonamido group, an alkoxy group, an acyloquik group, a carbamoyl group, a sulfamoyl group, and an alkoxy Among these, hydrogen atoms, substituted or unsubstituted alkyl groups, acylamino groups, sulfonamido groups, carbamoyl groups, and alkoxycarbonyl groups are most preferred. It is also very preferable that R4R6 is a hydroxyl group.

It is very preferable that m is 1, and it is relatively preferable that n is 0.

The total number of carbon atoms of R1-R8 in general formula (I) is l-
The number is preferably 16 or more, and more preferably 16 or more.

Specific examples of the compounds included in the general formula (I) of the present invention are listed below, but the present invention is not limited thereto.

(J) 1 (JH (2) The compounds of the present invention can be synthesized by the following synthesis examples and methods analogous thereto.

Synthesis Example 1-t(λ,!-dimethoxy3'-nitrobe/
Synthesis of siphenone) Place 372 m-nitrobensoyl chloride and p-dimethoxybenzene λtoy in a 31-meter three-way flask,
Methidichloride: Dissolve in y/, tl.

Aluminum chloride JOOI is added over about 1 hour while stirring at room temperature. The reaction mixture generated a little heat and the methylene chloride started to reflux. After stirring for about 2 hours, the mixture was left in the apparatus overnight.

The reaction mixture is poured into ice/~, the layers are separated, the methylene chloride/layer is separated, the solvent is distilled off on a steam bath, and the residue is poured into water/l while hot, crystals precipitate out.

After reading the water intake, ethanol/,! Recrystallize the product to obtain the desired product≠707 as pale yellow crystals. Melting point r0C0 Synthesis Example/-2 (Synthesis of 2,j-dimethoxy-3'-aminobenzohydrol) Into a stirring autoclave of 21, the intermediate IOO synthesized in /-/ and 10% palladium on carbon catalyst 2F were added. Fill with ethanol/, 31. After replacing the inside of the vessel with hydrogen twice, hydrogen was introduced under pressure at 100~/Crn2. Under stirring/J
Heat to 00C and continue stirring for r hours. −After cooling at night,
After opening the container and discharging the catalyst, the solution is concentrated to dryness. When 70xl of ethanol is added to the residue, white crystals are precipitated. Air dry several times to obtain the desired object. Melting point/32~
Hiroshi (Ic0 Synthesis Example/-3 (Synthesis of 2,j-dimethoxy-3'-aminodiphenylmethane) Acetic acid JOOrdf is placed in a No. 21 Mitsuro flask, and zinc powder 6y is gradually added while stirring vigorously.

Then, the intermediate synthesized in /-≠ri and jy- are introduced. Heat to tooc and add 3J% hydrochloric acid 24L0- to l1
Drips in minutes. After stirring for 30 minutes, add 3 more! Thihydrochloric acid λ4/-
Drop 0 ttl. After stirring for 2 hours at an internal temperature of 0'C, cool, remove the supernatant, and neutralize with an aqueous sodium hydroxide solution (NaOH7 (7j', water 600 yd) until the pH reaches 100%. The precipitated oily substance is dissolved in ethyl acetate. Extract with water, wash 6 times with deuterium chloride water, and dry with sodium sulfate. After filtration and concentration, evaporate under reduced pressure (boiling point / 70 ~ / 7z 0C / /
mHg). The fraction is poured into a Petri dish and crystallized to obtain the target product 317.

Melting point r/~t≠QC0 Synthesis example/-≠ (Synthesis of J, j-dihydroxy-3'-aminodiphenylmethane) Intermediate 27F synthesized in /-3 and 4L 4% hydrobromic acid co101 in volume/l When mixed in an eggplant flask, a platform will precipitate. When the mixture is refluxed for 1-2 hours at an oil bath temperature of 1-0°C in a nitrogen stream, the salt dissolves and a light brown solution is formed. Crystals will precipitate when cooled with ice, so separate them separately. A number of crystals/l
The mixture is placed in a beaker, dissolved in water λooxl, and neutralized by adding sodium acetate to liberate the amine. After air drying several times, it is recrystallized from a mixed solvent of ethanol and benzene (3/3) to obtain the desired product/6F. Melting point/! l~/
12°C.

Synthesis example/-Yo (Synthesis of dihydroxy-3'-laurylamide diphenylmethane) The intermediate ljP synthesized in 7-≠ was added to 300td Mitsuro 72 Sco with pyridi7 A d , acetonitrile 30yx
l, added with dimethyl acedoabado JOrxl and stirred while lauroyl chloride/4c,! P'ft is gradually dropped. After stirring for / hour, add hydrochloric acid water (10 d of 77% hydrochloric acid, 1 d of water)
ood) and continued stirring, the separated oil gradually crystallizes. After optical crystallization, the number of units, washing with water,
Dry to obtain 2 tons of the desired product. Melting point/22-j °C0 Synthesis example/-t (Synthesis of exemplified compound (6)) In a JOOxl three-way flask/-! Intermediate 26ftCt synthesized by
)-butanol λ4LP1 ethyl acetate/J 0rtl
Add concentrated sulfuric acid λ7° while stirring! d gradually. After the dropwise addition, the mixture was heated to Jj0C and stirred for μ hours. The reaction solution was poured into a beaker containing ice water and 200 tttl of gold to separate the layers, and ethyl acetate 1 was washed with water three times.

After drying over magnesium sulfate overnight, ethyl acetate was distilled off under reduced pressure and a mixed solvent of n-hexane and ethyl acetate (λ0:/)/
30- to obtain the desired white crystals /i,ty. Elemental analysis value calculated as melting point 1y-i~kooC002gH43NO3 (%)
C; 7J, 7r H; P, jj N: j, OY actual measurement value (%) C; 7A, j co H; ri/N
; J, 02 Synthesis Example a-/(Synthesis of (≠-octanesulfonamidophenethyl)hydroquinone) (4t-aminophenethyl)hydroquinone 10OF with dimethylacetamide! With 00x11 pyridine 3Axl/! Place it in a Mitsuro flask and add octane sulfonyl chloride r! while stirring at room temperature. d gradually.

After the dropwise addition, stirring was continued for μ hours, and the reaction solution was poured into hydrochloric acid water.
Extract with ethyl acetate, wash with water, dry over magnesium sulfate, and concentrate to obtain the desired product/λFP1 as an oil.

Synthesis Example Coco (Synthesis of α value of exemplified compound) Into a Mitsuro flask, place the intermediate/2 1 synthesized in Co 2 together with ethyl acetate≠00ml, and add concentrated sulfuric acid JOwl dropwise to the water-cooled bottom stopper (JO0C below). Then λ-methyl-7-
Butene/1rOtd was added dropwise, stirred at room temperature for 72 hours, and then left overnight. The reaction solution is poured into aqueous hydrochloric acid, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and concentrated.

The product is purified by silica gel column chromatography using a mixed solvent of chloroform and ethyl acetate (λ0:/) as a developing solution, and then concentrated to obtain the target product 10ty as a pale brown oil.

Calculated elemental analysis value as C27H4□N04S (%)
C; 61. /7 H; 1.1. WN;
2. Actual measurement value (%) C; 6F,! /H:1
．． l, ON; ko, 113 The amount of the reducing agent added in the present invention is silver 1
0°00/~λO mole, particularly preferably 0
,0/~/Q mol. Also, 0.0 per mole of the reducible dye-donating substance! -10 mol, particularly preferably 0.1-3 mol.

It is also possible to use a combination of the reducing agent of the present invention and a known reducing agent.

Examples of known reducing agents include U.S. Pat.
Columns ≠ 2-10 of λ6, No. 3, No. 3, No. 3Q-31 of No. 3, No. 330.

1.17, 4c,! No. 90,112, Japanese Patent Publication No. 1983
-/Hiro 0333, pages (I7) to (/1), j7-
1402≠j number, same j4-/JI7J1 number, same jy-i
7r4czr issue, 5r-z3r issue, ii issue, same! Tar/
124Alfi No. 2, same jter/124tjO,
Same 40-//2111, same jO-/ur from Hiro 36 to Hiro 3, same 60-/'? rjuO
Issue, same AO-/r/7 Hiroλ issue, same 6/-2! European Patent No. 220, European Patent No. 220
There are reducing agents and reducing agent precursors described in, for example, pages 7r-22 of No. 7 HirotA1.

Since the reducing agent of the present invention has low diffusivity, the reducing agent of the present invention (
It is preferred to use a combination of electron transfer agents and/or electron transfer agent precursors to facilitate electron transfer between the electron donor (electron donor) and the available silver halide.

The electron transfer agent or its precursor can be selected from the reducing agents or precursors thereof described above. It is desirable that the mobility of the electron transfer agent or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor).

Particularly useful electron transfer agents are l-phenyl-3-pyrazolidones or aminephenols.

The combination of electron donor and electron transfer agent of the present invention is preferably incorporated into a color photosensitive material.

Electron donors, electron transfer agents, or their precursors can each be used in combination with an adhesion of λ or more. etc.), it can be added only to some emulsion layers, it can be added to layers adjacent to the emulsion (anti-scratching layer, undercoat layer, intermediate layer, protective skin, etc.), or it can be added to all emulsion layers. It can also be added to the layer. The electron donor and electron transfer agent can also be added to the same layer. Also, these reducing agents can be added in the same layer as the dye-donating compound or in a separate layer, but the diffusion-resistant electron donor is not present in the same layer as the dye-donating compound. is preferred.

The electron transfer agent can be incorporated into the receiving material (dye fixing layer), or if a solvent is present during development, it can be dissolved in the solvent.

The reducible dye-providing compound used in the light-sensitive material of the present invention is disclosed in U.S. Pat.
It is a non-diffusible compound that reacts with the reducing agent that remains unoxidized during development and releases a diffusible dye, as described in 7-Hiro 4A2, Kokai Technical Report t7-67P, etc.

Examples include U.S. Pat. A compound that releases a diffusible dye by an intramolecular nucleophilic substitution reaction after being reduced, as described in No. 13333 and No. 7-411-11J-3, etc. No. 107, Japanese Patent Publication No. 10/641'5', A/-412
! No. 7, RD2'fi02Z (1999), etc., a compound that releases a diffusible dye by an intramolecular electron transfer reaction after being reduced, West German Patent No. J, oor,
zrrA, JP-A-/≠koj30, U.S. Patent No.≠, 34L3,193, U.S. Patent No. tt, tty, rr4c
A compound whose single bond is cleaved after reduction to release a diffusible dye, as described in US Patent No. ≠, 4c! 0.
Nitro compounds that release diffusible dyes after electron acceptance, as described in US Pat. No. 123 and others, US Pat.

Examples include compounds that release a diffusible dye after accepting electrons, as described in No. 60, No. 60, and the like.

Also, as a very preferable example, European Patent No. 220.7
Hiroshi, No. 6A4, Public Technical Report r7-615#, Special Application ShojJ-
Compounds having an N-X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in No. 34AWjJ, No. 42-317P111, etc., patent application No. 1983
5o2-x(x
has the same meaning as above) and an electron-withdrawing group, a compound having a po-x bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in Japanese Patent Application No. 10TRRIYO,
In one molecule, c-
x' bond (X' is synonymous with X or represents -5O2-)
and a compound having an electron-withdrawing group.

Among these, compounds having an N-X bond and an electron-withdrawing group in the -molecule are particularly preferred. Specific examples thereof include compounds (I) to (3), (
7) ~(Isu, (I2), (I3), (I5), (23
)～(26),(3su,(32),(35),(36)
, (40), (41), (4s, (53) to (59),
(64), (70), and Compounds (I1) to (23) of Kokai Technical Report 17-J/Tata.

Hydrophobic additives such as dye-donating compounds and the diffusion-resistant reducing agents of the present invention can be incorporated into one of the photosensitive elements by known methods such as those described in U.S. Pat. Can be done. In this case, % Kaisho 5r-r3ija issue,
JP-/711AJ/No., JF-/714112, JP-771 Hiroyo 3, Doyoter/71≠j≠,
Same jter/7r4Ajj issue, same! A high-boiling point organic solvent such as that described in 71 #j No. 7 may be used in combination with a low-boiling point organic solvent having a boiling point of 0 cm 14° C., if necessary. 2!0 as a high boiling point organic solvent
The viscosity at C is 10 centipoise or more! 8 tolerance rate is 1
Compounds with 0 or less are preferred. Examples include:

Viscosity Dielectric constant (n-C14H290-) P=0 /r9cp Hiroshi, 0/ Viscosity Dielectric constant The amount of high boiling point organic solvent is the dye-donating compound used/g
10g or less, preferably 1g or less. In addition, /CC or less with respect to binder /g, and even 0,7
cc or less, especially 0 or JCC or less is suitable.

Special public Sho J/-Jri No. 163, Japanese Patent Public Sho J1-J Tata 443
The dispersion method using polymers described in No.

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

Various surfactants can be used when dispersing hydrophobic compounds in hydrophilic colloids. For example, Tokukai Shojp
-/j7AJj, pages (37) to (3t), those listed as surfactants can be used.

The light-sensitive material of the present invention basically contains a photosensitive silver halide, a binder, a reducing agent, a reducible dye-providing compound, and a high-boiling organic solvent on a support. These components are often added to the same layer, but they can also be added separately to separate layers if they are in a reactable state.

For example, if a colored dye-providing compound is present in the lower layer of the silver rhodanide emulsion, a decrease in sensitivity can be prevented. When the reducing agent is added not only to the emulsion layer but also to the intermediate layer, color reproducibility is improved.

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

For example, there are combinations of three layers such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can have various arrangement orders known for regular color photosensitive materials.

Further, each of these photosensitive layers may be divided into two or more layers as necessary.

The light-sensitive material of the present invention can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antennary layer, and a back layer.

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

The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent and a photofog. It may also be a so-called Co-El emulsion in which the inside of the grain and the surface layer of the grain have different phases.

Halogen (arsenal emulsion may be monodisperse or polydisperse, or a mixture of monodisperse emulsions may be used. The grain size is 0.1-
λμ, especially O0λ~/, 6μ is preferred. ) The crystal habit of the silver rhodanide grains may be cubic, monohedral, /≠hedral, tabular with a high astral aspect ratio, or any other form.

Specifically, U.S. Pat.
Column, No. 621.0λ/issue, Research Disclosure Magazine (hereinafter abbreviated as RD) 77029 (I77
1 year), Japanese Patent Publication No. 12-2j3/j? Any of the silver rhodanide emulsions described in No. 1, etc. can be used.

Although the silver halide emulsion may be used as it is, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, well-known sulfur sensitization methods, reduction sensitization methods, metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-λj3/!2).

The coating amount of photosensitive silver rhodanide used in the present invention is in the range of 1 to 10 g/nL2 in terms of silver.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver rhodanide.

Among such organic metal salts, organic silver salts are particularly preferably used as organic compounds that can be used to form organic silver salt oxidizing agents described in Uchi's book, U.S. Patent No. 100.

626 No. 62~! There are benzo) IJ azoles, fatty acids and other compounds described in column 3, etc. Also, JP-A-60
-// Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in the evening issue of 323, and JP-A No. 6
Acetylene silver described in No. 7-2 Hiro'Pogur is also useful. Two or more types of organic silver salts may be used in combination.

The above organic silver salt contains 7 mol of photosensitive silver halide,
o, oi to io mole, preferably O0O/ to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is calculated in terms of silver! ON9 or iog/
m2 is appropriately -1.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD/71
Azoles and azaindenes described in pages 2 to 4Aj (/7 to 2005), nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-1999-1999-ITR Gluco, or JP-A-6F- ///Mercapto compounds and metal salts thereof described in AJ7, acetylene compounds described in JP-A-62-17917, and the like are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopolar cyanine pigments,
Included are cyanine dyes, steryl dyes and hemioxonol dyes.

Specifically, U.S. Patent No. ≠, G/7. ．． 2j7 issue, Tokukai Sho! Examples include sensitizing dyes described in RD/10j No. 10, RD/10j No. 17033j, and RD/70 Kota (1999)/pages 2 to 13.

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

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in US Pat. , 411.

6, No. 1, Patent Application No. 62, etc.).

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening, or as disclosed in U.S. Patent No. 1I,/l'
No. 3,714, I-, 226. It may be carried out before or after nucleation of silver halide grains according to No. tAt. The amount added is generally about lo-8 to IQ-2 moles per mole of silver halide.

A hydrophilic binder is preferably used for the constituent layers of the photosensitive material or dye fixing material. An example of this is JP-A-62-. Examples include those described on pages (26) to (2t) of 2jJ/, issue t. Specifically, transparent or translucent hydrophilic binders are preferred, such as proteins such as gelatin and gelatin derivatives, or cellulose derivatives,
Natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan, etc. and polyvinyl alcohol,
Examples include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Also, JP-A-62-
Super absorbent polymers described in 2Hiroj 260, etc., i.e. homopolymers of vinyl monomers having -COOM or -803M (M is a hydrogen atom or an alkali metal) tl-, or these vinyl monomers are combined with other vinyl monomers. Copolymers of (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-jH manufactured by Sumitomo Chemical Co., Ltd.) are also used. Two or more of these binders can also be used in combination.

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

In the present invention, the binder application lid is 92% per 7m2.
The amount is preferably 0 g or less, particularly 10 g or less, and more preferably 7 g or less.

Constituent layers (including back layers) of photosensitive materials or dye-fixing materials contain various polymers for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. It can contain latex. Specifically, Japanese Patent Application Laid-Open No. 6.2-λll-6231, voice J12
Any of the polymer latexes described in -/El, 1, Hiro issue, t2-iiotta issue, etc. can be used. In particular, using a polymer latex with a low glass transition point (tlo0c or lower) for the mordant layer can prevent cracking of the mordant layer, and using a polymer latex with a high glass transition point for the back layer can prevent curling. It will be done.

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds preferably used, see U.S. Patent No. ≠, 10.
No. 0.626! l~! It is written in the λ column.

In systems that form images by diffusion transfer of dyes, dye fixing materials are used together with photosensitive materials. The dye fixing material may be coated separately on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive material. The relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer is described in U.S. Patent No. μ.

! 00.1Gu No. 4! The relationship described in column 7 is also applicable to the present application.

It has at least seven layers of N containing a mordant and a binder, preferably used in the present invention. As the mordant, those known in the photographic field can be used, and specific examples include those described in U.S. Pat. OO, AJ No. 4 whistle ~ ty column and JP-A-4/-411λj1. Whistle (32) ~ (4=/
), the mordant described in JP-A-42-. 2 Guru O≠No. 3,
Examples include those described in tλ--≠Hiroshi No. 036. Further, dye-receiving polymeric compounds such as those described in U.S. Pat.

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

In particular, it is useful to provide a protective layer.

A high boiling point organic solvent can be used in the constituent layers of the light-sensitive material and the dye-fixing material as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive material and the dye-fixing material. Specifically, there are those described in Japanese Patent Publication No. 2003-120002, page (λj) of issue No. 31 of JP-A No. 6, No. 6, No. 2≠j2!3, and the like.

Furthermore, various silicone oils (
All silicone oils can be used, from dimethylsilicone oil to modified silicone oils in which various organic groups are introduced into dimethylsiloxane. For example,
Various modified silicone oils, especially carboxy-modified silicone (product name X-21-3
7IO) etc. are effective.

Also, Japanese Patent Application Publication No. 1986/1983/JRIJ3, Japanese Patent Application No. 1982-2 J
The silicone oil described in Ar No. 7 is also effective.

Antifading agents may be used in the photosensitive materials and dye fixing materials. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A/-/JRI 6≠≠ are also effective.

Benzotriazole compounds (
U.S. Patent No. J,! 73! .
42-
There are compounds described in /366 Hiroshi No. 1, Hiroshi No. 6/-rrxzt, etc. Further, the ultraviolet absorbing polymer described in JP-A-62-2t01J-2 is also effective.

Examples of metal complexes include U.S. Pat. ≠, 1st issue No. 3~ column, JP-A-62-17 Hiroshi 7≠1
No. A/-41211. There are compounds described in Japanese Patent Application No. 61-23-103, Japanese Patent Application No. 6u-31OP4, Japanese Patent Application No. 1.2-230!94, and the like.

Examples of useful antifading agents are described in JP-A-6.2-2/jλ72 (/2j) to (/37).

The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material from outside the photosensitive material. .

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

A fluorescent whitening agent may be used in the photosensitive material or dye fixing material. In particular, it is preferable that the fluorescent whitening agent is placed inside the dye-fixing material or supplied from outside the photosensitive material. An example of this is “The
Chemistry of 5ynthetic D
yes J Volume V No. RG, JP-A-1. /-/≠37jλ
Examples include compounds described in No.

Specifically, sterbene compounds, coumarin compounds, biphenyl compounds, and benzene compounds. Examples include sazolyl compounds, naphthalimide compounds, pyrazoline compounds, and carbosteryl compounds.

Optical brighteners can be used in combination with antifade agents.

Hardeners used in constituent layers of photosensitive materials and dye-fixing materials are described in U.S. Pat. 2-//At,! ! Examples include hardeners described in No. 1, No. 24/1, No. 4/-/I, No. 4c, and the like.

Specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinylsulfonyl hardeners (N + N'-ethylene-bis(vinylsulfonylacetamide) ether, / etc.), N-
Examples include methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in #Kai-Sho 62-Co3≠/J7, etc.).

Various surfactants can be used in constituent layers of photosensitive materials and dye fixing materials for purposes such as coating aids, improving peelability, improving slipperiness, preventing static electricity, and promoting development. Specific examples of surfactants are given in JP-A No. 62-17 JIItJ, No. 6-7.
13 Hiro! It is stated in No. 7 etc.

The constituent layers of photosensitive materials and dye-fixing materials include improved slipperiness,
An organic fluoro compound may be included for the purpose of preventing static electricity and improving peelability. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 7-2 Ojj No. t to No. 17;
No. 209'A, same tλ-73! Examples include fluorine-based surfactants such as those described in No. rλ6, and hydrophobic fluorine compounds such as oil-like fluorine-based compounds such as fluorine oil, or solid fluorine-containing compound resins such as tetra7tethylene resin.

A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, silicon dioxide, polyolefin or polymethacrylate can be used.
In addition to the compounds described on page 6 (2), penzoguanami/
Patent application for resin beads, polycarbonate resin beads, AS resin beads, etc. Showa 2-/100/, If No. 62-
/1004! There are compounds described in this issue.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, colloidal silica, and the like. Specific examples of these additives
It is described on pages 11214 whistle (26) to (3 pages).

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive material layers. sb has functions such as promoting the transfer of dye from the dye to the dye fixing layer, and from a physicochemical function, bases are base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, and surfactants. It is classified as a compound that interacts with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. For details of these, see U.S. Pat.
．． It is written in 73 ri whistle 3t-≠O grab.

Examples of base precursors include salts of organic acids and bases that are thermally decarboxylated, compounds that release a-groups by intramolecular nucleophilic substitution reactions, Rossen rearrangement, or Peckman rearrangement. Specific examples thereof are described in U.S. Pat.

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

In addition to the above, combinations of poorly soluble metal compounds and compounds that can undergo complex formation reactions with metal ions constituting the poorly soluble metal compounds (referred to as complex-forming compounds) and special Kaisho Otsu/-232≠! 7
Compounds that generate bases by electrolysis, such as those described in this issue, can also be used as base precursors. The former method is particularly effective. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

The light-sensitive material and/or dye-fixing material of the present invention always has a constant t despite fluctuations in processing temperature and processing time during development.
Various development stoppers can be used for the purpose of obtaining a III image.

The term "development stopper" as used herein refers to a compound that immediately neutralizes or reacts with a base to lower the base concentration in the film and stop development after proper development, or a compound that interacts with silver and silver salts to prevent development (fik It is an inhibitory compound.

Specifically, an acid precursor that releases formic acid upon heating;
Examples thereof include electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, nitrogen-containing heterocyclic compounds, mercapto compounds, and precursors thereof.

For more details, see JP-A-6.2-263/J-ri No. (31)~
It is described on page (32).

As a support for the light-sensitive material or dye-fixing material of the present invention, one that can withstand processing temperatures is used. Common examples include paper and synthetic polymers (films). Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene/, polypropylene,
Polyimide, cellulose (e.g., triacetyl cellulose) or films containing pigments such as titanium oxide, film-processed synthetic paper made from polypropylene, synthetic resin pulp such as polyethylene, etc. Mixed paper made from and natural norzo, Yankee paper, baryta paper, coated paper (especially cast coated paper), metal, cloth, glass, etc. are used.

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

In addition to this, % Kaisho 62-koj3/! No. ri (2ri) to (3
/) can be used.

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

Methods for recording images by exposing them to photosensitive materials include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or negative film using a printer or enlarger, and copying. A method in which the original image is scanned and exposed through a slit etc. using a machine's exposure device, etc. A method in which the image 1 & 2 information is exposed by emitting light from a light emitting diode, various lasers, etc. via an electric signal, A method in which image information is transmitted to a CRT or liquid crystal display There is a method of outputting the image to an image display device such as a display, an electroluminescence display, or a plasma display, and exposing the image directly or through an optical system.

Light sources for recording th images on photosensitive materials include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, and the like as described in US Pat. No. 44,!
00, No. 426, the light source described in the whistle column can be used.

Further, it is also possible to convert the image into one image by using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the electric field and other materials that appear when a strong optical electric field such as a laser beam is applied, such as lithium niobate, potassium dihydrogen phosphate, etc. (KDP), lithium iodate, f3 af3204, etc., urea derivatives, nitroaniline derivatives, such as 3-
Methyl-≠-nitropyridine-N-oxide (POM)
Nitropyridine-N-oxide derivatives such as JP-A-Sho A/-! Compounds described in J Koko No. 2 and No. 6 Koko 10≠3λ are preferably used. As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both are useful.

The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), and images obtained by dividing an original image into a large number of pixels using a scanner. Signal, CG%C
Image signals created using a computer such as AD can be used.

The photosensitive material and/or the dye-fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

In this case, the transparent or opaque heating element is
/-l≠j The one described in the Hiroki specification etc. can be used. Note that these conductive layers also function as antistatic layers.

Current IIt! (and/or transfer) processing temperature is approximately 700℃
The heating temperature can be set arbitrarily above 0, but especially when using heat development, the heating temperature should be about 100C to about 2! Although it can be developed at O0C, about to 0c to about lro 0c is particularly useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed. The latter place,
The heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature, but it is particularly preferable to set the temperature at JO0C or higher and about io''c lower than the temperature in the heat development process.

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

Also, JP-A ShojP-2/IQ'fiJ No. 6/-23
10! 1, No. 1, etc., a method in which development and transfer are performed simultaneously or successively by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method, the heating temperature is preferably at least JO0C and at most the boiling point of the solvent; for example, when the solvent is water, it is preferably at least JO'C and at most 1000C.

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

These solvents can be used in a method of applying them to dye fixing materials, photosensitive materials, or both.

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

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-/≠72 Hirohiro, page (corresponding issue). Further, the solvent can be incorporated in advance into the photosensitive material, the dye fixing material, or both, such as by encapsulating the solvent in microcapsules.

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

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

Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material.

Heating methods in the development and/or transfer process include heating in contact with a heated block or plate, a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared and far-infrared heater/heater, etc. This may include contacting the device or passing it through a high-temperature atmosphere.

As for the pressure conditions and the method of applying pressure when the light-sensitive material and the dye-fixing material are superimposed and brought into close contact, the method described in JP-A-J/-/Ko 7 Co. 4t≠ (Core) page can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, Tokukai Akira! Turf 32 Hiro No. 7,
Same, Tar 1771≠No.7, same! Tar/No. 11313, 4O-1rY! The apparatus described in Japanese Utility Model Application Publication No. 42-2jYIAlt, etc. is preferably used.

The color photosensitive material of the present invention may be designed to be processed by a so-called normal wet color diffusion transfer method. In this case, the above-mentioned photosensitive material and dye fixing material can be used, except for additives specific to heat development (eg, organic silver salt).

The base and electron transfer agent may be supplied from the processing solution in a rupturable container. A viscosity imparting agent and the like can be added to this treatment solution as is well known. Color diffusion transfer methods are well known in the art, and the present invention is applicable to any of these known means.

Example 1 The production method of emulsion (I) for the first layer will be described.

A well-stirred gelatin solution (water io.

Contains gelate 7209 and sodium chloride 32 in Qd7
AOOr+, an aqueous solution containing sodium chloride and potassium bromide (kept at 50C)! / and a silver nitrate aqueous solution (0.62 mol of silver nitrate dissolved in water AOOILt) were simultaneously added at equal flow rates over 30 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine rO mol %) with an average grain size of 0.3 jμ was prepared.

After washing with water and desalting, sodium thiosulfate j19 and ≠-hydroxy-6-mether/, J, 3a, 7-titrazaindene λ
Chemical sensitization was performed at t, o 0c by adding olv.

The yield of the emulsion was tooy.

Next, the method of preparing the emulsion (n) for the third layer will be described.

A well-stirred gelatin aqueous solution (contains gelatin-op and 3F sodium chloride in 1000w of water at 7!0C)
An aqueous solution containing sodium chloride and potassium bromide (AOOd) and a silver nitrate aqueous solution (600 J of water)
(in which silver nitrate o, r tamole was dissolved) and the following dye solution (I) were simultaneously added at equal flow rates over 10 minutes. In this way, the average particle size is 0.3! A monodisperse cubic silver chlorobromide emulsion (10 mol % of bromine) on which a μ dye was adsorbed was prepared.

Sodium thiosulfate after washing with water and desalting! Datobi-1 hydroxy-O-methyl/, J, Ja, 7-chitrazaindene λ
Chemical sensitization was performed at 60°C by adding oap. The yield of the emulsion was tooy.

Dye solution (I) Methanol Hiroshi00rdNext, the method of preparing the emulsion (III) for the third layer will be described.

A well-stirred gelatin solution (water io.

Dissolve gelatin powder Oy and ammonium in Qd (
1,000 td of an aqueous solution containing potassium iodide and potassium bromide and an aqueous silver nitrate solution (1 mole of silver nitrate dissolved in 10,100 O of water) were added at the same time while keeping the pAg constant. In this way, the average particle size O0! A monodisperse octahedral silver iodobromide emulsion (1 mol % of iodine) of μ was prepared.

Washing with water and desalting followed by auric acid (≠ water salt)! Gold and sulfur sensitization was performed at to 0c by adding sodium thiosulfate λda. The yield of the emulsion was /Kf.

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

Yellow dye-donating substance (I)* was weighed 1vy1, electron donor (I)* was weighed, tricyclohexyl phosphate was weighed, and ethyl acetate was 1It6! Add Lt, about 6
The mixture was heated and dissolved in O'C to form a homogeneous solution. This solution and 1 ooy of a 70% solution of lime-processed gelatin.

After stirring and mixing water t Oa: and sodium dodecylbenzenesulfonate i, ry, the mixture was dispersed using a homogenizer at 110,000 rpm for 70 minutes.

This dispersion is called a yellow dye-providing substance dispersion.

Dispersions of magenta and cyan dye-providing substances can be made using magenta dye-providing substance (2)* or cyan dye-providing substance (3) in the same way as dispersions of yellow dye-providing substances. Ta.

From these, photosensitive material 10/ having the structure shown in the following table was prepared.

In the photosensitive material 10/, the electron donor (I)* of the first, third and fifth layers of the present invention is shown in Table 1. Photosensitive materials 102 to io were prepared having the same structure as photosensitive material 10/, except that the equimolar amount was replaced with .

The reducing agent (I)* can be converted to BoIJ-v-(I) by the following method.
*Distributed and added.

Reducing agent m*/j and polymer (I)*7, J
P was dissolved in ethyl acetate≠Oxi at about AO°C to form a homogeneous solution. This solution, 1ooy of 70% aqueous solution of lime-treated gelatin, and J% aqueous solution of surfactant (5)*,
After stirring and mixing with Iyl, the mixture was dispersed using a homogenizer at 110,000 rpm for 10 minutes.

Next, we will discuss how to prepare the dye fixing material.

A color chart fixing material R-/ was prepared by coating on a paper support laminated with polyethylene according to the composition shown in the following table.

A tungsten light bulb is used for the color photosensitive material 10/-101 with the above-mentioned multilayer structure, and the density changes continuously. B, G
, R and Gray color separation filters at 100 lux for 1 second.

Water was supplied to the emulsion surface of the exposed light-sensitive material at an amount of 100 ml/in2 using a wire bar, and then the material was superimposed so that the dye-fixing material and the film surface were in contact with each other.

It was heated for 11 seconds using a heat roller whose temperature was adjusted so that the temperature of the absorbed film was Ijo (:).Next, when it was peeled off from the dye fixing material, the color separation of B, G, R, and gray appeared on the fixing material. Clear images of blue, green, red, and gray were obtained depending on the filter.

Table 2 shows the results of measuring the maximum density (Dmax) and minimum density (Dmin) of each color of cyan, maze/red, and yellow in the gray part.

Furthermore, the above color photosensitive material 1oi-ioz was stored for one week under the condition of μtoC relative humidity of 70%, and then processed in the same manner. The results are also shown in Table 1.

Example 1 Photosensitive material of Example 1 ioi~10! In the second layer,
Reducing agent (I) * Polymer (I) added to the intermediate layer of the first Hiro layer
)* and surfactant (5)* except for photosensitive material 20/
~20j was created. In addition, in the photosensitive materials 207 to 20, the intermediate layers of the second layer and the second layer are the first layer, third layer, and!, respectively. The same compound as the electron donor used in the layer is dispersed by the method described below as the reducing agent (I) of the photosensitive material 10/.
* Added in an equimolar amount to give a photosensitive material of 30/~30
! It was created.

21417 mol of each electron donor and high boiling point organic solvent (I)*
AjF was dissolved in 4AOxl of ethyl acetate at about to 0c to form a homogeneous solution. 1 of this solution and lime-treated gelatin
100y of 0% aqueous solution and 100y of 0% aqueous solution of surfactant (3)*/J, jd were stirred and mixed, and then dispersed with a homogenizer at 110,000 rpm for 70 minutes.

The photosensitive materials 20/-203 and 30/-30j were exposed to light using a spectrophotometer through a wedge whose density was continuously changing in the direction perpendicular to the wavelength, and the dye-fixing material of Example 1 was used. When processed in the same manner as 1, photosensitive material 20
/-20J- had insufficient color reproduction, but all of the photosensitive materials JO/-30j had good color reproduction.

Also, the photosensitive material oi-λQ! and JO/~30j≠
When the photographic properties of photosensitive materials 20/ and JOI were stored for a week at 70% relative humidity and compared with those immediately after preparation, Dmin increased significantly for photosensitive materials 20/ and JOI, but all other photosensitive materials exhibited poor photographic properties. There was little variation.

It has been found that by using the reducing agent (electron donor) of the present invention in the intermediate layer, color reproducibility can be improved and a photosensitive material with excellent storage stability can be provided.

Example 3 Using the same emulsion, dye-donating substance, electron donor, and electron transfer agent as in color photosensitive material 10/ of Example 1, a multilayer color photosensitive material Hiroshi 0/ having the structure shown in Table 3 was prepared.

Note that unless otherwise specified, the same additives as in Photosensitive Material 10/ were used.

The organic silver salt emulsion was prepared as follows.

Gelatin 20F and Hiro-acetylaminophenylpropiolic acid! , 1007% sodium hydroxide aqueous solution 10
It was dissolved in 100O and ethanol 200rd. This solution was kept at ≠0°C and stirred.

Silver nitrate in this solution! A solution of 1 dissolved in 200 ml of water was added over 3 minutes. Excess salt was then removed by sedimentation. Thereafter, the pH was adjusted to 6.3 to obtain an organic silver salt dispersion with a yield of 3ooy.

Further, antifoggant precursor (I)* having the following structure was added by Q twice the mole amount to the dye-donating substance, and dispersed in oil together with the dye-donating substance and the electron donor by the method of Example 1.

Photosensitive material 4AO/ except that equimolar amounts of the compound (A) or (co) of the present invention were added in place of the electron donor (I)* used in the first layer, third layer, and first layer. Photosensitive materials Hiroko and Hiro03 having the same configuration as ≠07
It was created.

Next, the method of preparing the dye fixing material (R-, 2) will be described.

Poly(methyl acrylate-N,N,N-)dimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is /:I) was dissolved in 2001111 water and treated with 70% lime. It was mixed uniformly with 1 oz of gelatin.

A hardening agent was added to this mixed solution, and the mixture was uniformly coated to a wet film thickness of 0 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample is used as a dye fixing material (R-λ) having a mordant layer.

After exposure in the same manner as in Example 1, it was heated uniformly for 30 seconds on a heat block heated to /≠00C.

7m on the membrane side of the dye fixing material (R-2) 20x
After supplying 1 of water, the heat-treated photosensitive materials were stacked on the fixing material so that the film surfaces were in contact with each other.

After that, the linear velocity lλml is applied to the simulator heated to ro0c.
After passing through the dye for 20 seconds, both materials were ground to obtain a positive image on the dye-fixing material.

Dma of each color of gray, some cyan, maze/red, and yellow
x was measured. Further, the above photosensitive materials 4t0/~≠03 were stored for a week under the condition of ≠z Oc relative humidity of 70%, and then processed in the same manner, and the photographic properties were compared with those processed immediately after preparation. Photosensitive material≠0/Dmin in forced test
Although there was a large increase in the photographic properties of the light-sensitive materials 4tO and 03, there was only a small change in photographic properties. It has been found that the storage stability of photosensitive materials can be improved by using the reducing agent (electron donor) of the present invention.

EXAMPLE Photosensitive material 10/ was prepared by sequentially coating the following layers on a transparent polyethylene terephthanate support.

Note that unless otherwise specified, the same additives as in Photosensitive Material 10/ were used.

cyan dye-donor layer containing a thick dye-receiving layer containing a white reflective layer containing a red-sensitive layer containing an opaque layer containing an intermediate layer containing a magenta dye-donor layer containing a green-sensitive layer (IX) the same intermediate layer as (■) Yellow dye-donor layer (XI) a') containing emulsion (III) (0.3g/7
7L2) b) Gelatin (including gelatin in a) above/
, /g/m) C) Blue-sensitive layer (■) containing surfactant (I) * (0,2 g/m2) a) Latex of polyethylene acrylate (θ
, Rig/rn ) b) Tenubin Co,! g/door) C) Hardener triacyloyl perhydrotriazine (Q
, O 4 g/m") d) Gelatin (/, jg/7n) e) Surfactant (I) * (0, -z g/n2) ) layer, (■) layer, (X
) The compound of the present invention (
It is a photosensitive material except that equimolar amounts of I) are added! A photosensitive material 102 having a composition similar to that of Ol was prepared.

The following layers were then sequentially coated onto a transparent polyethylene terephthalate film to prepare a cover sheet.

Acid neutralization layer (n) containing cellulose acetate (saccharification degree !Hiroshi%) Timing layer (III) coated with a thickness of 2 microns Copolymerized latex of vinylidene chloride and acrylic acid coated with a thickness of ≠ 2 microns For the tie layer, a treatment solution having the following composition was also prepared.

Potassium hydroxide 4'rgHiro-Hydroxymethyl-μmMethyl-/-P-tolyl-3pyrazolidinone 10g j-) f Rubenzenotria 7'-Rhaj g Sodium sulfite ha! g potassium bromide
7g benzyl alcohol 6.1g carbon black 110g water
The whole amount/! Quantity-sensitive material that can be used! After exposure to 0/10 λ through a wedge, the sheet was overlapped with a cover sheet, and a pair of juxtaposed rollers was used to uniformly spread the treatment liquid therebetween to a thickness of 10 μ.

The results of sensitometry performed 1 hour after the treatment are shown in the following table.

Furthermore, when the photosensitive materials zoi and jO were stored under 4At' (relative humidity 79%) conditions for one week and then processed in the same manner, and compared with those processed immediately after preparation, Dm
There was almost no variation in ax, but ])min
The increase in photosensitive materials! 0λ was smaller than that of the photosensitive material jO/. It has been found that the storage stability of photosensitive materials can be improved by using the reducing agent of the present invention.

Claims (1)

[Scope of Claims] 1) At least a photosensitive silver halide, a binder, a reducible dye-providing compound and the following general formula (
A color photosensitive material having a reducing agent represented by I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 and R^2 are hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, aryl groups, acylamino groups, alkoxy groups, respectively. , an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfonyl group, a carbamoyl group, or a sulfamoyl group, and R^1 and R^2 may jointly form a carbocycle. R
^3 represents an unsubstituted or alkyl group-substituted alkylene group. R^4, R^5, R^6, R^7, R^8 are hydrogen atoms, halogen atoms, cyano groups, nitro groups, substituted or unsubstituted alkyl groups, acylamino groups, sulfonamide groups, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, acyl group, acyloxy group, carbamoyl group, carbamoylamino group, sulfamoyl group, sulfamoylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic group, alkoxy It represents a sulfonyl group or an aryloxysulfonyl group, and R^4, R^5, and R^6 may be hydroxyl groups. Further, two adjacent rings may jointly form a carbocycle or a heterocycle. X represents -CO- or -SO_2-, and m and n each independently represent 0 or 1. The total number of carbon atoms in R^1 to R^8 is 8 or more.