JPH0545825A - Color diffusion transfer photosensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity in the color diffusion transfer photosensitive material and to lower minimum density corresponding to high exposed part by forming a positive image by using a combination of a diffusion-resistant compd. (positive dye doner) and a negative type silver halide emulsion releasing the diffusive dye reversely in accordance with reduction of silver halide to metallic silver. CONSTITUTION:The color diffusion transfer photosensitive material uses a reductive dye donor is allowed to release a diffusive dye by being reduced and represented by formula and a silver halide grain chemically sensitized by a selenium sensitizer. On the formula, PWR-(Time)t-Dye in which PWR is a group to be allowed to release (Time)t-Dye by reduction; Time is a group to release the dye or its precursor by the following reaction; and t is 0 or 1.

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 light-sensitive material, and more particularly to a diffusion resistant compound which releases a diffusible dye in reverse reaction to a reaction in which silver halide is reduced to silver. And a conventional negative-working silver halide emulsion to form a positive image.

More particularly, it relates to a color diffusion transfer photosensitive material which forms the above-mentioned positive image having high sensitivity and low minimum density.

[0003]

2. Description of the Related Art As a method for directly forming a positive image by a color diffusion transfer method, A) a direct positive silver halide emulsion and a diffusible dye corresponding to a reaction in which silver halide is reduced to silver are used. A method using a combination of a diffusion-resistant compound (referred to as a negative dye-donor compound) to be released, and B).
A diffusion-resistant compound or a silver halide emulsion, which becomes diffusive in response to a normal silver halide emulsion (a silver halide emulsion having a negative-positive response) and a reaction in which silver halide is reduced to silver, is prepared. There is a method of using a combination of diffusion-resistant compounds (which are referred to as positive dye-donor compounds) that release diffusible dyes corresponding to the reaction of being reduced to silver.

In the method A), for example, British Patent Nos. 1,3
No. 30,524, Japanese Patent Publication No. 48-39165, U.S. Pat. Nos. 3,443,940, 4,474,867, and 4,483,914, etc. A compound having a coupler (1), which releases a diffusible dye by a coupling reaction with an oxidized form of a reducing agent (D
DR coupler), U.S. Pat. No. 3,928,312,
No. 4,053,312, No. 4,055,428, No. 4,336,322, etc., it is reducible to silver halide, and when silver halide is reduced, it is diffusible. A compound that releases a dye (DRR compound) is used.

In the method B), US Pat. Nos. 3,134,764 and 3,362 are used.
819, 3,597,200, 3,544,5
45, 3,482,972, etc.,
A dye developing agent in which a hydroquinone-based developer and a dye component are linked (the dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide), US Pat. No. 4,503. , 137, etc., which release a diffusible dye in an alkaline environment but lose its ability when reacted with silver halide, and described in US Pat. No. 3,980,479, etc. Releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described above, a compound releasing a diffusible dye by an intramolecular rewinding reaction of an isoxazolone ring described in US Pat. No. 4,199,354, and the like. Patent No. 4,559,290, European Patent No. 22
0,746A2, U.S. Pat. No. 4,783,396,
A non-diffusible compound described in Japanese Unexamined Patent Publication No. 87-6199 which releases a diffusible dye by reacting with a reducing agent left unoxidized by development is used.

Among the above-mentioned two methods, the method B) is preferable in that high sensitivity can be easily obtained. However, the method B) has a problem that it is difficult to reduce the density of the lowest density portion which is particularly important in image formation.

In the method B), the dye-releasing reaction between the reducible dye-donor compound and the electron donor and the oxidation of the electron donor by the oxidant of the electron transfer agent (generated by the development of the photosensitive silver halide). The competition reaction and the reaction determine the density of the lowest density area (corresponding to the high exposure area) of the positive image.

Therefore, in order to reduce the minimum density with high sensitivity, the development of the photosensitive silver halide is controlled,
There is a need for a technique that optimizes the production of oxidants of electron transfer agents.

For the above-mentioned purpose, it is considered to be effective means to improve the development progress of the photosensitive silver halide. As a concrete method of these, tabular grains are used as silver halide grains. Method to be used (Japanese Patent Application No. 2-28251)
No. 3) or a method utilizing a high silver chloride emulsion (Japanese Patent Application No. 2-300305). However, these are not yet sufficient, and when the size of silver halide grains is increased in order to realize high sensitization, the progress of development is deteriorated and the minimum density is increased. Therefore, it has been desired to realize a method having both high sensitivity and excellent development progress.

[0010]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is to overcome the above-mentioned problems and form a color diffusion transfer for forming a positive image with high sensitivity and low minimum density and good color reproducibility. It is to provide a light-sensitive material.

[0011]

The above object is to provide a support having at least one photosensitive silver halide emulsion layer in combination with a dye image-forming material and an electron donor, the dye image-forming material comprising: Halogen comprising at least one reducible dye-donating compound represented by the following general formula (I), which releases a diffusible dye when reduced, and which is contained in at least one emulsion layer of the silver halide emulsion layer. It was achieved by a color diffusion transfer light-sensitive material characterized in that silver halide emulsion grains were chemically sensitized by a selenium sensitizer.

General formula (I) PWR- (Time) _t -Dye In the formula, PWR is reduced to give-(Tim).
e) represents a group releasing _t- Dye, and Time is PWR
Represents a group which is released as-(Time) _t -Dye and then releases Dye through a subsequent reaction, and t is 0.
Alternatively, it represents an integer of 1, and Dye represents a dye or a precursor thereof.

The present invention will be described in detail below. A feature of the present invention is that a silver halide emulsion chemically sensitized with a selenium sensitizer is used.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher, for a certain period of time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
No. 2, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-22930
It is preferable to use the compounds described in No. 0 and the like. Specific unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (eg,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium. And so on.

Preferred types of labile selenium compounds have been mentioned above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and play no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used.

As the non-labile selenium compound used in the present invention, Japanese Patent Publication Nos. 46-4553 and 52-34.
The compounds described in JP-B No. 492 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof.

Of these selenium compounds, preferred are the compounds represented by the following general formulas (I) and (II). General formula (I)

[0018]

[Chemical 1]

In the formula, Z ₁ and Z _{2, which} may be the same or different, each represent an alkyl group (for example, a methyl group,
Ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg, vinyl group, propenyl group), aralkyl group (eg, benzyl group, phenethyl group), aryl group (eg, phenyl group, penta) Fluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoylphenyl group, α-
Naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group, furyl group, imidazolyl group), -NR
₁ (R _2), - represents the OR ₃ or -SR _4.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. As the alkyl group, aralkyl group, aryl group or heterocyclic group, similar examples of Z ₁ can be mentioned.

However, R ₁ and R ₂ are hydrogen atoms or acyl groups (for example, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4 -Trifluoromethylbenzoyl group).

In the general formula (I), Z ₁ preferably represents an alkyl group, an aryl group or —NR ₁ (R ₂ ), and Z ₂
Represents -NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R
₆ may be the same or different, a hydrogen atom,
It represents an alkyl group, an aryl group, or an acyl group.

In the general formula (I), more preferably N, N-
Dialkylselenourea, N, N, N'-trialkyl-
N'-acyl selenoureas, tetraalkyl selenoureas,
Represents N, N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide.

General formula (II)

[0025]

[Chemical 2]

In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, -OR ₇ , -NR ₈ (R ₉ ), -SR. ₁₀ , -Se
Represents R ₁₁ , -X or a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or hydrogen. Represents an atom, and X represents a halogen atom.

In the general formula (II), Z ₃ , Z ₄ , Z
_The aliphatic group represented by ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aralkyl group (for example, a methyl group,
Ethyl group, n-propyl group, isopropyl group, t-butyl group, n-butyl group, n-octyl group, n-decyl group,
n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group,
A propargyl group, a 3-pentynyl group, a benzyl group, a phenethyl group).

In the general formula (II), Z ₃ , Z ₄ , Z
_The aromatic group represented by ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed ring aryl group (for example, a phenyl group, a pentafluorophenyl group, a 4-chlorophenyl group, 3- A sulfophenyl group, an α-naphthyl group, and a 4-methylphenyl group).

In the general formula (II), Z ₃ , Z ₄ , Z
_The heterocyclic group represented by ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom. Heterocyclic groups (eg, pyridyl group, thienyl group, furyl group,
Thiazolyl group, imidazolyl group, benzimidazolyl group).

In the general formula (II), the cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom or a bromine atom. Or represents an iodine atom.

In the general formula (II), preferably Z ₃ and Z ₄
Alternatively, Z ₅ represents an aliphatic group, an aromatic group or —OR ₇ , and R ₇ represents an aliphatic group or an aromatic group. General formula (I
In I), more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate.

Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the invention is not limited thereto.

[0034]

[Chemical 3]

[0035]

[Chemical 4]

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8]

[0040]

[Chemical 9]

[0041]

[Chemical 10]

The silver halide emulsion used in the present invention is subjected to various chemical sensitizations on the grain surface of the silver halide emulsion in combination with the chemical sensitization with the above-mentioned selenium sensitizer.
The above-mentioned chemical sensitization is described by James, The Theory of
Photographic Process, 4th Edition, published by Macmillan, 1977, (TH James, The Th
eory of the Photographic
Process, 4th ed, Macmillan,
1977) 67-76 and using active gelatin, and Research Disclosure 120, April 1974, 12008;
Research Disclosure, Vol. 34, June 1975.
Mon, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, 4,266. , 018, and 3,904,415.
No. 1,315,755 and pAg 5-10, pH 5-8 and temperature 30-
It can be carried out at 80 ° C. using selenium used in the present invention, or sulfur, tellurium, gold, platinum, palladium, iridium, rhodium or a combination of a plurality of these sensitizers.

The method of using the selenium sensitizer used in the present invention will be described in detail below. The above selenium sensitizer is dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or in Japanese Patent Application No. 2-2644.
No. 47, No. 2-264448, and added at the time of chemical sensitization. It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination.
The unstable selenium compound and the non-unstable selenium compound may be used in combination.

The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, etc.
It is preferably 1 × 10 ⁻⁸ mol or more per mol of silver halide. More preferably 1 × 10 ⁻⁷ mol or more and 1 × 10
^-5 mol or less. The temperature of chemical ripening when the selenium sensitizer is used is preferably 45 ° C. or higher. It is more preferably 50 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, the effect of the present invention can be obtained in a wide pH range of 4 to 9.

The selenium sensitization is more effective when carried out in the presence of a silver halide solvent. Examples of the silver halide solvent that can be used in the present invention include US Pat.
No. 1,157, No. 3,531,289, No. 3,5
74,628, JP-A-54-1019, 54-1.
(A) Organic thioethers described in JP-A-58917, JP-A-53-82408 and JP-A-55-77737.
(B) thiourea derivatives described in JP-A No. 55-2982, and (c) a thiocarbonyl group embedded between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. Silver halide solvent having
(D) imidazoles, (e) sulfite, (f) thiocyanate and the like described in JP-A No. 4-100717.

Particularly preferred solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1 × per mol of silver halide.
It is 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less.

The chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound, or in the presence of a sulfur-containing compound such as hypo, a thiourea compound and a rhodanine compound.

The sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time. Also, gold sensitization is usually
It is carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time.

For sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allyl isothiocyanate, cystine, p-
Toluenethiosulfonate, rhodanine and the like can be mentioned. Other U.S. Pat. Nos. 1,574,944 and 2,
410,689, 2,278,947, 2,728,668, 3,501,313, 3,656,955, 3,857,711,
Nos. 4,054,457 and 4,266,018, German Patent 1,422,869, Japanese Patent Publication No. 56-
The sulfur sensitizers described in JP-A-24937, JP-A-55-45016 and the like can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature and size of silver halide grains, but is 1 × 10 ^-7 mol or more per 5 mol of silver halide and 5 × 10 ^-4. It is preferably not more than mol.

As the gold sensitizer for the above-mentioned gold sensitization, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like.

The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is 1 × 10 ^-7 per mol of silver halide.
It is preferably not less than 5 and not more than 5 × 10 ⁻⁴ mol. Upon chemical ripening, a silver halide solvent and a selenium sensitizer or a sulfur sensitizer which can be used in combination with a selenium sensitizer and / or
Alternatively, there is no particular limitation on the timing and order of addition of the gold sensitizer, and for example, the above compounds may be added at the same time as the initial (preferably) chemical ripening or during the chemical ripening, or at different addition points. can do. In addition, at the time of addition, an organic solvent capable of mixing the above compound with water or water, for example, methanol, ethanol,
It may be added after being dissolved in a single liquid such as acetone or a mixed liquid.

Regarding the selenium sensitization method, US Pat.
No. 74944, No. 1602592, No. 16234
No. 99, No. 3297446, No. 3297447
No. 3320069, No. 3408196, No. 3408197, No. 3442653, No. 34.
No. 20670, No. 3591385, French Patent No. 2693038, No. 2093209, Japanese Patent Publication No. 52
-34491, 52-34492, and 53-29.
5, 57-22090, and JP-A-59-18053.
No. 6, No. 59-185330, No. 59-181337.
No. 59-187338 and No. 59-192241.
Issue No. 60-150046, Issue No. 60-151637
No. 61-246738, JP-A-3-42221,
Japanese Patent Application Nos. 1-287380, 1-250950, 1-254441, 2-334090 and 2-11
No. 0558, No. 2-130976, No. 2-13918
No. 3, No. 2-229300, and British Patent No. 255.
No. 846, No. 861984, and H.M. E. Spec
er et al., Journal of Photograph
Hic Science, Vol. 31, pp. 158-169 (1983).

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid to be used, compounds such as azaindene, azapyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aids are:
US Pat. Nos. 2,131,038 and 3,411,91
4, 3,554,757, JP-A-58-1265.
No. 36, JP-A No. 62-253159 and Daffin's "Photographic Emulsion Chemistry", pages 138-143 (published by Focal Press, 1966).

In addition to chemical sensitization, US Pat.
As described in 1,446 and 3,984,249, reduction sensitization can be performed by using, for example, hydrogen, and U.S. Pat. Nos. 2,518,698 and 2,74.
3,182 and 2,743,183 with stannous chloride, thiourea dioxide, polyamines and such reducing agents, or at low pAg (eg less than 5) or high pH (eg Reduction sensitization can be carried out by treatment. U.S. Pat. No. 3,91
The chemical sensitization methods described in 7,485 and 3,966,476 can also be applied.

Further, JP-A-61-3134 and 61-3
The sensitizing method using an oxidizing agent described in JP-A No. 136 can also be applied.

In the present invention, various forms of silver halide emulsions can be used. Examples of them are regular particles having regular crystal bodies such as cubes, octahedra and tetradecahedrons, tabular grains, spherical grains, grains having irregular crystal shapes such as potato grains, etc. Can be mentioned.

The silver halide composition of these grains is any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodide, and silver chloride. May be used, but silver bromide or silver chlorobromide is preferred. Further, it may contain silver thiocyanate, silver cyanate and the like.

The silver halide composition in the grains may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. (JP-A-5
7-154232, 58-108533, 58
-248469, 59-48755, 59-5
2237, U.S. Pat. Nos. 3,505,068 and 4,
433,048, 4,444,877, European Patent 100,984, and British Patent 1,027,14.
No. 6)

The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.01 μ to 10 μ, and particularly preferably 0.1 μ to 3 μ. Here, a monodisperse silver halide emulsion is defined as 95% or more of the total weight or the total number of silver halide grains contained therein is within ± 40% of the average grain size, more preferably within ± 30%. To be done.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research
Disclosure magazine (hereinafter abbreviated as RD) 1702
9 (1978) and any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

Two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions, etc. can be used in combination, and they are used in different emulsion layers and / or the same emulsion layer. It is possible to

In the present invention, it is particularly advantageous to use tabular silver halide grains. Regarding tabular silver halide grains, U.S. Pat. No. 4,434,226 has already been mentioned.
Nos. 4,439,520 and 4,414,310
No. 4,433,048, 4,414,306
No. 4,459,353, JP-A-59-99433.
No. 62-209445 and the like, the manufacturing method and the use technique thereof are disclosed.

Further, JP-A-63-220238 and JP-A-1-201649 disclose tabular silver halide grains in which dislocations are intentionally introduced. The ratio of the average grain diameter to the average grain thickness in tabular grains (hereinafter referred to as grain diameter / thickness) is preferably 2 or more, and 3 to
It is preferably 12 and particularly preferably 5-8.

The grain diameter / thickness can be obtained by averaging the grain diameters / thicknesses of all tabular grains. A simple method is to use the average diameter of all tabular grains and the average thickness of all tabular grains. It can also be calculated as the ratio with.

The tabular grains have a diameter (corresponding to a circle) of 0.3 μm or more, preferably 0.3 to 10 μm, more preferably 0.
5 to 5.0 μm, more preferably 0.5 to 2.0 μm
Is.

The grain thickness is less than 1.0 μm, preferably 0.05 to 0.5 μm, more preferably 0.08 to
It is 0.3 μm. In the present invention, the tabular grains account for 50% or more of the projected area of all grains in the emulsion containing the tabular grains. Preferably 70% or more, more preferably 9
It is 0% or more.

The grain diameter and grain thickness of the tabular grains can be measured by electron micrographs of the grains as described in US Pat. No. 4,434,226. Specific examples of the halogen composition of tabular grains include silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, and silver chloroiodobromide. Alternatively, silver chlorobromide is preferred. It may also contain silver thiocyanate, silver cyanate and the like.

Further, in the present invention, the tabular grains are preferably monodisperse. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-151618.

In the tabular grains, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver thiocyanate and oxides. .. These emulsion grains are described in U.S. Pat.
142,900, 4,459,353, British Patent 2,038,792, U.S. Patent 4,349,62.
No. 2, No. 4,395,478, No. 4,433,501
No. 4,463,087, No. 3,656,962
No. 3,852,067, JP-A-59-16254.
No. 0 and the like.

The silver halide grains used in the present invention are
Graphide, Physics and Chemistry of Photography, published by Paul Montel (P. Glafkides, Chimie et P.
hysique Photographique, Pa
ul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi).
n, Photographic Emulsion C
chemistry, Focal Press, 196
6), "Manufacturing and Coating of Photographic Emulsions" by Zecriman et al., Published by Focal Press (VL Zelikman et.
al, Making and Coating Pho
topographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the above regular grains can be obtained by controlling the pAg and pH during grain formation. For details, see, for example,
Science and Engineering (Photog
radical Science and Engine
ering), Volume 6, 159-165 (196)
2); Journal of Photographic Science (Journal of Photographics)
c Science), Volume 12, pp. 242-251 (1
964), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748.

Regarding the monodisperse emulsion, JP-A-48-
No. 8600, No. 51-39027, No. 51-8309
No. 7, No. 53-137133, No. 54-48521.
No. 54-99419, No. 58-37635, No. 58-49938, Japanese Patent Publication No. 47-11386, US Pat. No. 3,655,394 and British Patent No. 1,41.
3, 748 and the like.

During the production of an emulsion containing tabular grains, a silver salt solution (eg AgNo) added to accelerate grain growth.
₃ aqueous solution) and a halide solution (eg KBr aqueous solution)
A method of increasing the addition rate, the addition amount, and the addition concentration of is preferably used. Regarding these methods, for example, British Patent No. 1,335,925 and US Pat.
900, 3,650,757, 4,242,4
45, JP-A-55-142329 and JP-A-55-158.
The description of No. 124 can be referred to.

A silver halide solvent is useful for promoting the ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Therefore, introduction of a halide salt solution into the reactor can accelerate aging. Other ripening agents can be used, and the total amount of these ripening agents can be mixed in the dispersion medium in the reactor before adding the silver and halide salts, and one or more ripening agents can be used. It is also possible to add a halide salt, a silver salt or a deflocculant, and to introduce them into the reactor. As another variation, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264.
Nos. 2,448,534 and 3,320,06
Instructions can be found in No. 9. US Pat. No. 3,271,1
57, 3,574,628 and 3,73
Conventional thioether ripening agents as described in 7,313 can also be used. Alternatively, JP-A-53-
The thione compounds as disclosed in No. 82408 and No. 53-144319 can also be used.

The properties of the silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor. In addition, one or more salts can be added together with the salt according to a conventional method. US Patent Nos. 2,448,060 and 2,628,167
Issue 3, Issue 3,737,313, Issue 3,772,031
Issue, and Research Disclosure, Vol. 134,
June 1975, 13452, copper, iridium, lead, bismuth, cadmium, zinc, (sulfur,
The properties of silver halide can be controlled by allowing compounds such as chalcogen compounds such as selenium and tellurium), gold and compounds of Group VII noble metals to be present during the silver halide precipitation formation process. Japanese Patent Publication 58-1410
Issue, Moisar et al., Journal of Photographic Science, 25, 1977.
As described on pages 19 to 27, the silver halide emulsion can reduce-sensitize the inside of the grain during the precipitation formation process.

The silver halide grains used in the present invention are
Usually, those which have been physically aged, chemically aged and spectrally sensitized are used. Additives used in such a process are Research Disclosure No. 17643 (197)
8) and the same No. 18716 (1979).

As the protective colloid used when preparing the emulsion of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, A wide variety of synthetic hydrophilic polymeric substances such as single or copolymers such as polyvinylpyrazole can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan, No. 16, P30 (1966)
You may use the enzyme-processed gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described on pages 24 to 25 of RD17643 (1978), JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, mercapto compounds and metal salts thereof described in JP-A-59-111636, acetylene compounds described in JP-A-62-87957 and the like can be used.

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

Specifically, US Pat. No. 4,617,25
7, JP-A-59-180550 and JP-A-60-1403.
No. 35, RD17029 (1978) pages 12 to 13 and the like.

These sensitizing dyes may be used alone, or a combination thereof may be used, and a combination of sensitizing dyes is often used particularly for the purpose of supersensitization. A dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light, together with a sensitizing dye,
A compound exhibiting supersensitization may be contained in the emulsion (for example, U.S. Pat. No. 3,615,641 and JP-A-63-231).
45, etc.).

These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or in accordance with US Pat. Nos. 4,183,756 and 4,225,666, the core of silver halide grains may be added. It may be before or after formation. In particular, the presence of a sensitizing dye at the time of chemical sensitization often gives a preferable effect.

The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide. Useful sensitizing dyes used in the present invention are, for example, US Pat. No. 3,522,05.
No. 2, No. 3,619,197, No. 3,713,828
Issue No. 3,615,643 Issue 3,615,632
No. 3,617,293, 3,628,964
No. 3,703,377, No. 3,666,480
Issue 3, Issue 3,667,960, Issue 3,679,428
No. 3,672,897, No. 3,769,026
Issue 3,556,800, Issue 3,615,613
Issue No. 3,615,638 Issue No. 3,615,635
Issue 3,705,809, Issue 3,632,349
Issue 3, Issue 3,677,765, Issue 3,770,449
Issue 3, Issue 3,770,440, Issue 3,769,025
Issue No. 3,745,014 Issue No. 3,713,828
No. 3,567,458, No. 3,625,698
No. 2, 526, 632, No. 2, 503, 776
No. 48, JP-A-48-76525, Belgian Patent No. 69
No. 1,807 and the like.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ³ in terms of silver.

Next, each component included in the present invention will be described. (A) Support The support used in the present invention is a transparent support, a white support, a black support or the like which is usually used as a smooth photographic support. The thickness of the transparent support is 50 to 350 μm,
Preferably, polyethylene terephthalate, cellulose acetate, polycarbonate or the like having a thickness of 70 to 210 μm is used. In order to prevent light piping, the transparent support may contain a slight amount of pigment such as titanium dioxide and a trace amount of paint.

The term "white support" as used in the present invention means a support having a white side on which at least the dye image-receiving layer is coated, and any support having sufficient whiteness and smoothness can be used. Can be done. For example, particle size 0.1 to 5 μm
Titanium oxide, barium sulphate, zinc oxide and other white pigments are added and stretched to form microvoids, which causes whitening of polymer films, such as polyethylene terephthalate, polystyrene, and polypropylene films and synthetic films formed by conventional sequential biaxial stretching. Paper, or paper obtained by laminating polyethylene, polyethylene terephthalate, polypropylene, or the like on both sides of paper, is preferably used. A white pigment such as titanium white may be kneaded in the laminate layer.

The thickness of the support is 50 to 350 μm, preferably 70 to 210 μm, more preferably 80 to 150 μm.
m. If necessary, a light-shielding layer can be provided on the support. For example, a support obtained by laminating polyethylene containing a light-shielding agent such as carbon black on the back surface of a white support is used.

As the black support, polyethylene terephthalate, cellulose acetate, polycarbonate, polystyrene containing a light shielding agent such as carbon black and having a thickness of 50 to 350 μm, preferably 70 to 210 μm,
A thickness of 50 to 400 μm, preferably 70 including a light shielding agent such as polypropylene or carbon black.
It is preferable to use polyethylene, polyethylene terephthalate, polypropylene or the like laminated on both sides of a paper support having a thickness of up to 250 μm.

As the carbon black raw material, for example, D
onnel Voest "Carbon Black"
Marcel Dekker Inc. , (1976)
Any manufacturing method such as a channel method, a thermal method and a furnace method as described in 1. can be used. The particle size of carbon black is not particularly limited, but is 90-
It is preferably 1800Å. The addition amount of the black pigment as the light-shielding agent may be adjusted depending on the sensitivity of the light-sensitive material to be shielded, but it is preferably about 5 to 10 in terms of optical density.

When a black support is used or when the whiteness of the white support is insufficient, it is necessary to provide a white light reflecting layer between the support and the dye image-receiving layer, and the particle size is 0.1. It is preferable to provide a layer containing a white pigment such as titanium oxide, barium sulfate, or zinc oxide having a thickness of up to 5 μm, or a hollow polymer latex.

(B) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming substance is provided. The constituent elements other than the silver halide emulsion will be described below. (1) Dye image-forming substance The dye image-forming substance used in the present invention (hereinafter referred to as a reducible dye-donating compound) does not itself release a dye in connection with silver development, but it is a dye when reduced. Is to be released. This type of compound can be used in combination with an electron donor to release an imagewise diffusible dye upon reaction with the remaining electron donor which has been imagewise oxidized by silver development. For the atomic group having such a function, see, for example, US Pat. Nos. 4,183,753 and 4,1.
42,891, 4,278,750, 4,13
9,379, 4,218,368, JP-A-53-
110827, U.S. Pat. Patent No. 4,783,396
Issue, open technical report 87-6199, European Patent Publication No. 220,
746A2 and the like.

The reducing dye-providing compound used in the present invention is preferably a compound represented by the following general formula (I). General formula (I) PWR- (Time) _t -Dye In the formula, PWR is reduced to give-(Tim).
e) represents a group that releases _t- Dye. Time is PWR
Represents a group that is released as-(Time) _t -Dye and then releases Dye through a subsequent reaction. t is 0
Or represents an integer of 1. Dye represents a dye or a precursor thereof.

First, the PWR will be described in detail. P
WR is US Pat. Nos. 4,139,389 and 4,13.
9,379, 4,564,577, JP-A-59-
As disclosed in Japanese Patent No. 185333 and No. 57-84453, a moiety containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound which releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced. Or US Pat. No. 4,232,107, JP-A-59-101649, Research Disclosure (1984) IV, 24025 or JP-A-61-1.
As disclosed in 88257, it corresponds to an electron-accepting quinonoid center and a portion containing a carbon atom linking it to a photographic reagent in a compound that releases the photographic reagent by an electron transfer reaction in the molecule after reduction. It may be one. Further, JP-A-56-142530,
U.S. Pat. Nos. 4,343,893 and 4,619,88
As disclosed in No. 4, an aryl group substituted with an electron-withdrawing group in a compound in which a single bond is cleaved after reduction to release a photographic reagent and an atom (a sulfur atom or a carbon atom or It may correspond to a portion including a nitrogen atom). U.S. Pat. No. 4,450,
No. 223, which may correspond to a nitro group in a nitro compound that releases a photographic reagent after accepting an electron and a portion containing a carbon atom connecting the nitro group and the photographic reagent, and US Pat. No. 4,609,610, which corresponds to a geminal dinitro moiety in a dinitro compound that beta-eliminates a photographic reagent after electron acceptance and a part containing a carbon atom connecting the nitro reagent to the photographic reagent. Is also good.

Further, a compound having SO ₂ --X (X represents oxygen, sulfur or nitrogen) and an electron-withdrawing group in one molecule described in US Pat. No. 4,840,887,
PO in one molecule described in JP-A-63-271344
A compound having an -X bond (X is the same as above) and an electron-withdrawing group, a C-X 'bond (X' is synonymous with X or -SO in one molecule described in JP-A-63-271341. _2- represents) and a compound having an electron-withdrawing group.

In order to more fully achieve the object of the present invention, among the compounds of general formula (I), those represented by general formula [CII] are preferred.

[0099]

[Chemical 11]

(Time) _t -Dye is R ¹⁰¹ , R ¹⁰²
Alternatively, it binds to at least one of EAGs. The part corresponding to PWR in the general formula [CII] will be described.

X is an oxygen atom (-O-) or a sulfur atom (-S).
-) Or a group containing a nitrogen atom (-N (R ¹⁰³ )-). R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent a group other than a hydrogen atom or a mere bond.

Examples of the group other than the hydrogen atom represented by R ¹⁰¹ , R ¹⁰² and R ¹⁰³ include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a sulfonyl group, a carbamoyl group and a sulfamoyl group. Yes, these may have a substituent.

R ¹⁰¹ and R ¹⁰³ are preferably substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups and the like. The carbon number of R ¹⁰¹ and R ¹⁰³ is preferably 1 to 40.

R ¹⁰² is a substituted or unsubstituted acyl group,
A sulfonyl group is preferred. The number of carbon atoms is preferably 1-40. R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may combine with each other to form a 5- to 8-membered ring.

Oxygen is particularly preferable as X. The EAG will be described later.

In order to achieve the object of the present invention, among the compounds represented by the general formula (CII), the compound represented by the general formula (CI
Those represented by II) are preferred.

[0107]

[Chemical formula 12]

(Time) _t -Dye is R ¹⁰⁴ , EAG
To at least one of the. X has the same meaning as described above. R ¹⁰⁴ represents an atom group which is bonded to X and a nitrogen atom to form a 5- to 8-membered monocyclic or condensed heterocycle including the nitrogen atom.

In the general formulas (CII) and (CIII), EAG represents a group that receives an electron from a reducing substance, and is bonded to a nitrogen atom. As EAG, a group represented by the following general formula (A) is preferable.

[0110]

[Chemical 13]

In the general formula (A), Z ₁ represents a group represented by Chemical formula 14 or> N-.

[0112]

[Chemical 14]

V _n represents an atomic group forming a 3- to 8-membered aromatic with Z ₁ and Z ₂ , and n represents an integer of 3 to 8. Specific examples of V _n are V ₃ ; -Z _3- , V ₄ ;-
_{Z 3 -Z 4 -, V 5} ; -Z 3 -Z 4 -Z 5 -, V 6; -
_{Z 3 -Z 4 -Z 5 -Z 6} -, V 7; -Z 3 -Z 4 -Z 5
_{-Z 6 -Z 7 -, V 8} ; -Z 3 -Z 4 -Z 5 -Z 6 -Z
₇ -Z ₈ - it is.

Z _{2 to} Z ₈ are each a group represented by Chemical formula 15,
A group represented by Chemical formula 16, -O-, -S-, or -S
Each represents O ₂ — and Sub represents a simple bond (pi bond), a hydrogen atom or a substituent described below.
In Chemical formula 16, even if each Sub is the same,
Further, they may be different from each other, or may be bonded to each other to form a 3- to 8-membered saturated or unsaturated carbocycle or heterocycle.

[0115]

[Chemical 15]

[0116]

[Chemical 16]

In the general formula (A), Sub is selected so that the sum of the Hammett substituent constants sigmapara of the substituents is +0.50 or more, more preferably +0.70 or more, and most preferably +0.85 or more.

EAG is preferably an aryl group substituted with at least one electron-withdrawing group, or a heterocyclic group. The substituent bonded to the aryl group or heterocyclic group of EAG can be used for controlling the physical properties of the entire compound. Examples of the physical properties of the entire compound, in addition to adjusting the electron acceptability, for example, water-soluble, oil-soluble, diffusible, sublimable, melting point, dispersibility in binders such as gelatin, reactivity to nucleophilic groups, It can be used to control the reactive groups for electrophilic groups.

A specific example of EAG is US Pat. No. 4,78.
No. 3,396, European Patent Publication No. 220,746A2, No. 6
~ Page 7.

Time represents a group which releases Dye through the subsequent reaction by using cleavage of nitrogen-oxygen, nitrogen-nitrogen or nitrogen-sulfur bond as a scratch. Various groups represented by Time are known, and for example, JP-A-61-1472.
No. 44, pages (5) to (6), Nos. 61-236549, (8) to (14), and groups described in JP-A No. 62-215270.

The dye represented by Dye may be an off-the-shelf dye, or alternatively a dye precursor that can be converted to a dye in a photographic processing step or an additional processing step, and the final image dye may be metal chelated. You don't have to. Representative dyes include metal chelated or non-metal chelated dyes such as azo dyes, azomethine dyes, anthraquinone dyes and phthalocyanine dyes. Among these, azo cyan, magenta and yellow dyes are particularly useful.

Examples of yellow dyes: US Pat. No. 3,59
7,200, 3,309,199, 4,01
3,633, 4,245,028, 4,15
6,609, 4,139,383, 4,19
5,992, 4,148,641, 4,14
8,643, 4,336,322, JP-A-51-
No. 114930, No. 56-71072, Research
ch Disclosure No. 17630 (19
78) and 16475 (1977).

Examples of magenta dyes: US Pat. No. 3,45
No. 3,107, No. 3,544,545, No. 3,93
2,380, 3,931,144, 3,93
No. 2,308, No. 3,954,476, No. 4,23
No. 3,237, No. 4,255,509, No. 4,25
0,246, 4,142,891, 4,20
7,104, 4,287,292, JP-A-52-
106727, 53-23628, 55-36.
804, 56-73057, 56-71060.
No. 55-134.

Examples of cyan dyes: US Pat. No. 3,482,
972, 3,929,760, 4,013,6
No. 35, No. 4,268,625, No. 4,171,22
0, 4,242,435, 4,142,891
Issue 4,195,994, Issue 4,147,544
No. 4,148,642, British Patent No. 1,551,
138, JP-A-54-99431 and JP-A-52-882.
No. 7, No. 53-47823, No. 53-143323.
No. 54-99431, No. 56-71061, European Patent (EPC) No. 53,037, No. 53,04.
No. 0, Research Disclosure N
o. 17630 (1978) and 16475 (1)
977).

As a kind of dye precursor, a diffusion-resistant dye-providing compound having a dye whose absorption spectrum is temporarily shifted can be used during storage and exposure of the light-sensitive material. A dye whose absorption spectrum is temporarily shifted (hereinafter referred to as a temporary shift dye) means a dye whose absorption spectrum is different from the original absorption spectrum when observed as an image. , The original absorption spectrum may be obtained at the same time as being emitted from the diffusion-resistant dye-providing compound, and the original absorption spectrum may be obtained independently of the emission at the time of development. The original absorption spectrum may be obtained after reaching.

The dyes used here include yellow, magenta, cyan, black and the like. When these dyes are structurally classified, nitro and nitroso dyes, azo dyes (benzeneazo dyes, naphthaleneazo dyes, heterocyclic azo dyes, etc.) ), Stilbene dye, carbonium dye (diphenylmethane dye, triphenylmethane dye, xanthene dye, acridine dye, etc.), quinoline dye, methine dye (polymethine dye, azomethine dye, etc.), thiazole dye, quinoneimine dye (azine dye, oxazine dye, Thiazine dyes, etc.), lactone dyes, aminoketone dyes, hydroxyketone dyes, anthraquinone dyes,
Examples thereof include indigo dyes, thioindigo dyes, and phthalocyanine dyes. Preferred temporary shift dyes are azo dyes, carbonium dyes, anthraquinone dyes, methine dyes, and quinoneimine dyes, and particularly preferred are azo dyes.

As a method for obtaining a temporary shift dye that can be used in the present invention, the dye is a two-electron reductant, and the original absorption spectrum is transferred to a hypsochromic color, and the original absorption spectrum is obtained by oxidation during or after the development processing. Method (azo dye, anthraquinone dye, methine dye, quinoneimine dye, indigo dye, etc.), the auxochrome is chemically blocked to shift the original absorption spectrum to a hypsochromic color, and deblocking is performed during development processing to achieve the original absorption. Spectral method [Chemical blocking method] (azo dye, carbonium dye, methine dye, etc.), or after reaching the image receiving layer, it is chelated with a metal ion to change to a dye having a desired absorption spectrum. Methods [post-chelation method] (azo dye, methine dye, phthalocyanine dye, etc.) Chemical blocking method and the post-chelate method in the bright is preferred.

Regarding these methods, in the method of chemically blocking the auxochrome, as an example in which the release and the deblocking of the dye occur independently, JP-A-57-158638 and JP-A-5-158638 can be used.
5-53329, 55-53330, and the like, and as a more general example of the method of other blocks, U.S. Pat. No. 4,009,02.
No. 9, No. 4,310,612, No. 3,674,478
No. 3,932,480, No. 3,993,661
No. 4,433,200, 4,363,865
No. 4,410,618. An example in which the release and deblocking of the dye occur at the same time is described as a specific example in US Pat. No. 4,783,396. Further, a method of changing to a dye having a desired absorption spectrum by chelating with a metal ion after reaching the image receiving layer is disclosed in JP-A-58-209742.
58-2020974, 58-17438, 5
8-17437, 58-17436, 57-1
85039, 57-58149, U.S. Pat.
204,993, 4,148,642, 4,1
47,544, JP-A-57-158637 and 58.
-123537, 57-181546, 60-
No. 57837, No. 57-182738, No. 59-20.
No. 8551, No. 60-37555, No. 59-1544.
No. 8, No. 59-149362, No. 59-164553.
An example is described in the issue.

The compound represented by the above general formula (CII) or (CIII) needs to be non-migrating in the photographic layer by itself, which is why EAG, R ¹⁰¹ , R ¹⁰² , R
It is desirable to have a ballast group having 8 or more carbon atoms at the ¹⁰⁴ or X position (particularly at the EAG position).

Typical specific examples of the reducible dye-providing compound used in the present invention are listed below, but the present invention is not limited to these and is described in US Pat. No. 4,783,396.
No., European Patent Publication No. 220,746A2, Public Technical Report 87
The dye-donor compounds described in -6199 and the like can also be used.

[0131]

[Chemical 17]

[0132]

[Chemical 18]

[0133]

[Chemical 19]

[0134]

[Chemical 20]

[0135]

[Chemical 21]

[0136]

[Chemical formula 22]

[0137]

[Chemical formula 23]

[0138]

[Chemical formula 24]

[0139]

[Chemical 25]

Each of these compounds can be synthesized by the methods described in the patent specifications cited above.
The amount of the reducing dye-providing compound used depends on the extinction coefficient of the dye, but is in the range of 0.05 to 5 mmol / m ² , preferably 0.1 to 3 mmol / m ² . The dye-donor compounds may be used alone or in combination of two or more. Also,
To obtain an image of black or different hue, Japanese Patent Application Laid-Open No.
No. 0-162251, for example, a cyan, magenta, and yellow dye-donating compound are mixed in a layer containing at least one type of silver halide or in an adjoining layer, and the mixture has a different hue. It is also possible to use a mixture of two or more dye-providing compounds that release a sex dye.

(2) Electron Donor In the present invention, an electron donor (when referred to as an electron donor in the present invention, a precursor thereof is used), the details of these compounds are described in US Pat. No. 4,783, 396
No., European Patent Publication No. 220,746A2, Public Technical Report 87
No. 6199 and the like. A particularly preferable electron donor is a compound represented by the following general formula (C) or (D).

[0142]

[Chemical formula 26]

In the formula, A ¹⁰¹ and A ¹⁰² each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group which can be deprotected by a nucleophile. Here, as the nucleophile,
OH ⁻ , RO ⁻ (R; alkyl group, aryl group, etc.),
Examples thereof include anionic reagents such as hydroxamic acid anions and SO ₃ ^2−, and compounds having unshared electron pairs such as primary or secondary amines, hydrazine, hydroxylamines, alcohols and thiols.

In the formula, when A ¹⁰¹ and A ¹⁰² represent a group which can be removed by an alkali (hereinafter referred to as a precursor group), it is preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group or oxazolyl. Groups, hydrolyzable groups such as sulfonyl groups, precursor groups of the type utilizing the reverse Michael reaction described in US Pat. No. 4,009,029, ring opening reaction described in US Pat. No. 4,310,612. A precursor group of the type which utilizes an anion generated later as an intramolecular nucleophilic group, and an anion described in US Pat. Nos. 3,674,478, 3,932,480 or 3,993,661 is conjugated. Precursor groups that transfer electrons through the system, thereby causing a cleavage reaction, in US Pat. No. 4,335,200. Precursor to cause cleavage reaction by electron transfer Hiraku Tamaki reaction anion of the mounting base or U.S. Pat. No. 4,363,865, the 4, 41
Precursor groups utilizing an imidomethyl group described in No. 0,618 are mentioned.

A ¹⁰¹ and A ¹⁰² are R when possible.
²⁰¹ , R ²⁰² , R ²⁰³ and R ²⁰⁴ may be bonded to each other to form a ring. Further, A ¹⁰¹ and A ¹⁰² may be the same or different.

R ²⁰¹ , R ²⁰² , R ²⁰³ and R ²⁰⁴ are each a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a flufamoyl group or an amide. Group, imide group, carboxyl group, sulfonamide group and the like. These groups may have a substituent if possible.

However, the total number of carbon atoms of R ^{201 to} R ²⁰⁴ is 8
That is all. In the general formula (C), R ²⁰¹ and R
²⁰² and / or R ²⁰³ and R ²⁰⁴ , in the general formula (D), R ²⁰¹ and R ²⁰² , R ²⁰² and R ²⁰³ and / or R ²⁰³ and R ²⁰⁴ are bonded to each other to form a saturated or unsaturated ring. You may.

Among the electron donors represented by the general formula (C) or (D), those in which at least two of R ^{201 to} R ²⁰⁴ are substituents other than hydrogen atom are preferable. Particularly preferred compounds are those in which at least one of R ²⁰¹ and R ²⁰² and at least one of R ²⁰³ and R ²⁰⁴ are a substituent other than a hydrogen atom.

A plurality of electron donors may be used in combination, or an electron donor and its precursor may be used in combination. Specific examples of the electron donor are listed, but the present invention is not limited to these compounds.

[0150]

[Chemical 27]

[0151]

[Chemical 28]

[0152]

[Chemical 29]

[0153]

[Chemical 30]

[0154]

[Chemical 31]

Although the amount of the electron donor used has a wide range,
Preferably 0.01 to 5 per mole of positive dye-donor compound
The preferable range is 0 mol, particularly 0.1 to 5 mol. Also, 0.001 mol to 5 mol per mol of silver halide
The molar amount is preferably 0.01 to 1.5 mol.

(3) Intermediate layer In addition to the diffusion-resistant electron donor as a reducing agent, in order to suppress stain of the positive image-forming light-sensitive material using such a reducible dye-donating compound, Although it is effective to use an electron transfer agent, the generated electron transfer agent radicals diffuse into other layers having different color sensitivities, cross-oxidize the electron donors there, and further accelerate fog development, There is a problem that the color reproduction deteriorates due to the decrease in density.

In order to solve these problems, an intermediate layer may be provided between photosensitive layers having different color sensitivities, or a diffusion resistant reducing agent may be contained in this intermediate layer. Specific examples thereof include non-diffusible hydroquinone, sulfonamide phenol, sulfonamide naphthol, and the like, and more specifically, JP-B Nos. 50-21249 and 50-2381.
3, No. 49-106326, No. 49-129535.
U.S. Pat. Nos. 2,336,327 and 2,360,
No. 290, No. 2,403,721, No. 2,544,6
No. 40, No. 2,732,300, No. 2,782,65
No. 9, No. 2,937,086, No. 3,637,393
No. 3,700,453, British Patent No. 557,75.
No. 0, JP-A-57-24941 and JP-A-58-21249.
No. etc. Further, regarding the dispersion method thereof, JP-A-60-238831 and JP-B-60-1897.
No. 8.

The amount used was 1 m for the support in each intermediate layer.
0.05 to 50 mmol per ² , binder 1
It is in the range of 0.01 to 50 mmol per g.
The method of adding the diffusion resistant reducing agent to the intermediate layer includes an oil dispersion method, a polymer dispersion method, a fine particle dispersion method and the like, and any method may be used.

Examples of the binder for the intermediate layer of the present invention include gelatin or gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, natural substances such as gum arabic, polyvinyl acetal (preferably having an acetalization degree of 20% or less, for example. Polyvinyl butyral), polyacrylamide, polyvinyl pyrrolidone, ethyl cellulose, polyvinyl alcohol (preferably,
Water-soluble polymers such as those having a saponification rate of 75% or more).

If desired, two or more kinds of these binders may be mixed and used.

Further, the intermediate layer of the present invention may contain solid particles. For example, various white pigments such as titanium dioxide, zinc oxide, calcium oxide, calcium carbonate, magnesium carbonate, barium sulfate, aluminum oxide, silicon dioxide, black pigments such as carbon black, and other organic and inorganic coloring pigments are used. can do. Further, ferrite, aluminum powder, metal powder such as copper powder, graphite powder and the like can be used.

Polymer particles can also be used as the solid particles of the intermediate layer of the present invention. If desired, these solid particles may be used in combination of two or more kinds. The average particle diameter of the solid particles contained is 0.005 μm to 1.
It is 0 μm, preferably 0.01 μm to 0.5 μm.

The content of solid particles in the intermediate layer of the present invention is
It is preferably 5% by weight or more, more preferably 20 to 100% by weight, based on the binder of the intermediate layer.

(4) Addition Method To introduce the dye-donor compound, the electron donor or its precursor and the other hydrophobic additive of the present invention into the hydrophilic colloid layer, a high-boiling point organic solvent such as alkyl phthalate ( Dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricyclohexyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg tributyl acetylcitrate), benzoic acid Acid esters (eg, octyl benzoate), alkylamides (eg, diethyllaurylamide), fatty acid esters (eg, dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (eg, trib trimesic acid) Chill), carboxylic acids described in JP-A-63-85633,
JP-A-59-83154, JP-A-59-178451,
59-178452, 59-178453, 59-178454, 59-178455, 5
9-178457, the method described in US Pat. No. 2,322,027, or an organic solvent having a boiling point of about 30 ° C. to 160 ° C., for example, a lower solvent such as ethyl acetate or butyl acetate. After dissolving in alkyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc.,
Dispersed in hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used. After dispersion, the low boiling point organic solvent may be removed by ultrafiltration or the like, if necessary.

The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the dye-donor compound used. Further, it is 5 g or less, preferably 2 g or less, relative to 1 g of the diffusion resistant reducing agent. Further, 1 g or less of the high-boiling organic solvent, preferably 0.5 g or less, and more preferably 0.3 g or less is suitable for 1 g of the binder.

Further, Japanese Patent Publication No. 51-39853, Japanese Patent Laid-Open No. 51-39
A dispersion method using a polymer described in JP-A-59943 can also be used. Alternatively, it may be dispersed directly in the emulsion, or may be dissolved in water or alcohol and then dispersed in gelatin or the emulsion.

In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. (For example, JP-A-59-174830
No. 53-102733, No. 63-271339, etc.) When dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157636, (37) to (3)
8) The surfactants listed on page 8 can be used.

(5) Construction of Photosensitive Layer For reproducing a natural color by the subtractive color method, the above-mentioned dye that 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 consisting of at least two layers with an image-forming substance is used. The emulsion and the dye image-forming substance may be coated as separate layers,
Alternatively, they may be mixed and coated as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity region of the emulsion combined with it, another layer is preferable. In this case, the layer of the reducible dye-providing compound is preferably located under the silver halide emulsion layer in terms of sensitivity. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image-forming substance layer. A partition layer described in JP-B-60-15267 is provided to increase the color image density, and JP-A-60-
It is also possible to increase the sensitivity of the photosensitive element by providing a reflective layer described in No. 91354.

In a preferred multilayer structure, a combination unit of blue-sensitive emulsion, a combination unit of green-sensitive emulsion and a combination unit of red-sensitive emulsion are sequentially arranged from the exposure side. When the present invention is used as a photographing material, an ultraviolet absorbing layer can be provided on the uppermost layer of the photosensitive layer.

For the absorption layer, various ultraviolet absorbers generally used in the technical field such as benzotriazole compounds, 4-thiazolidone compounds and benzophenone compounds can be used.

(C) Dye 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 may have a multi-layered structure in which mordants having different mordant strengths are applied in layers. Regarding this, JP-A-61-25255
No. 1 is described. As the mordant, a polymer mordant is preferable.

The polymer mordant used in the present invention is a polymer having a secondary or tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation group thereof, or the like and having a molecular weight of 5,000 or more. Particularly preferred is 10,000 or more.

For example, US Pat. No. 2,548,564
Issue 2, Issue 2,484,430, Issue 3,148,061
Nos. 3,756,814 and other vinyl pyridine polymers and vinyl pyridinium cation polymers; US Pat. No. 4,124,386 and other vinyl imidazolium cation polymers; US Patent Nos. 3,625,694, 3,859,
096, 4,128,538, British Patent Nos. 1,2
77,453 and other polymer mordants capable of crosslinking with gelatin and the like; US Pat. No. 3,958,9
No. 95, No. 2,721,852, No. 2,798,06
3, JP-A-54-115228 and JP-A-54-1455.
No. 29, No. 54-126027, No. 54-15583.
5, sol-type mordants disclosed in US Pat. No. 5,617,352; etc .; water-insoluble mordants disclosed in US Pat. No. 3,898,088; US Pat. No. 4,168,976. Reactive mordants capable of forming a covalent bond with the dyes disclosed in U.S. Pat. No. 4,201,840 and the like; and U.S. Pat. Nos. 3,709,690 and 3,7.
88,855, 3,642,482, 3,48
8,706, 3,557,066, 3,27
1,147, 3,271,148, JP-A-53-
No. 30328, No. 52-155528, No. 53-12
5, No. 53-1024, No. 53-107835,
Mention may be made of the mordants disclosed in British Patent 2,064,802.

Others, US Pat. No. 2,675,316
The mordants described in Nos. 2,882,156 can also be mentioned.

Of these mordants, those which do not easily move from the mordant layer to another layer are preferable, for example, those which undergo a crosslinking reaction with a matrix such as gelatin, water-insoluble mordant, and aqueous sol (or latex dispersion) type. Mordants are preferred. Particularly preferred is a latex dispersion mordant,
Particle size 0.01 to 2 μm, preferably 0.05 to 0.2 μm
m is better.

The coating amount of the mordant varies depending on the kind of the mordant, the content of the quaternary cation group, the kind and amount of the dye to be mordant, the kind of the binder used, etc., but it is 0.5 to 10 g / m 2.
² , preferably 1.0 to 5.0 g / m ² , and particularly preferably ² to 4 g / m ² .

As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and the like are used, and gelatin is preferred.

An anti-fading agent may be used in the image receiving layer. As the anti-fading agent, for example, an antioxidant, an ultraviolet absorber,
Or there is some kind of metal complex. These are substantially contained in the image receiving layer, but can be added to other layers as long as the effect can be obtained.

Examples of antioxidants include chroman compounds, coumarane compounds, phenol compounds (eg hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.),
4-thiazolidone compounds (U.S. Pat. No. 3,352,6
No. 81), benzophenone compounds (JP-A-46-
2784) and others, JP-A-54-48535,
There are compounds described in JP-A-62-136641, JP-A-61-188256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of the metal complex include US Pat. No. 4,24.
No. 1,155, No. 4,245,018, columns 3 to 36,
No. 4,254,195, columns 3 to 8, JP-A-62-17.
4741, 61-88256 (27) to (29).
Page, JP-A-1-75568, JP-A-63-19924.
There are compounds described in No. 8 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137). An anti-fading agent for preventing fading of the dye transferred to the image-receiving element may be contained in the image-receiving element in advance, or may be supplied to the image-receiving element from the outside such as a light-sensitive element or a processing composition. Good.

The above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination with each other.

A fluorescent whitening agent may be used in the light-sensitive element and the image-receiving element. In particular, whether a brightening agent is built into the image receiving element,
It is preferably incorporated in the light-sensitive element or the processing composition and supplied to the image-receiving element during the processing step. As an example,
K. Venkataraman ed. “The Chem
The compounds described in “Istry of Synthetic Dyes”, Volume V, Chapter 8, JP-A-61-143752 and the like can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned.

The fluorescent brightening agent can be used in combination with an anti-fading agent.

(D) 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 an alkali carried from the treatment composition, and is required. Depending on the situation, it may have a multi-layered structure including layers such as a neutralization rate adjusting layer (timing layer) and an adhesion enhancing layer. The preferred acidic substance is a substance containing an acidic group having a pKa of 9 or less (or a precursor group which gives such an acidic group by hydrolysis), more preferably olein described in US Pat. No. 2,983,606. Higher fatty acids such as acids, US Pat. No. 3,362,8
Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in No. 19; acrylic acid as disclosed in French Patent No. 2,290,699 Acrylic ester copolymers; US Pat. No. 4,139,383 and Research
Disclosure (Research Disclo
Sure) No. Mention may be made of latex-type acidic polymers as disclosed in 16102 (1977).

Others, US Pat. No. 4,088,493
No. 52-153739, 53-1023.
No. 53-4540, 53-4541, 53
The acidic substances disclosed in No. 4542 and the like can also be mentioned.

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

The above-mentioned polymer acid may be used alone or in combination with a hydrophilic polymer. Such polymers include polyacrylamide, polyvinylpyrrolidone,
Polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose,
Examples include hydroxyethyl cellulose and polymethyl vinyl ether. Of these, polyvinyl alcohol is preferable.

Further, a polymer other than the hydrophilic polymer, such as cellulose acetate, may be mixed with the polymer acid. The coating amount of the polymer acid is adjusted by the amount of alkali spread on the photosensitive element. The equivalent ratio of polymer acid to alkali per unit area is preferably 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stains are generated on the white background portion, and if it is too large, the hue is changed or the light resistance is deteriorated. A more preferable equivalent ratio is 1.0 to 1.3. When mixed with a hydrophilic polymer, too much or too little hydrophilic polymer will reduce photographic quality. The weight ratio of hydrophilic polymer to polymer acid is 0.
It is 1 to 10, preferably 0.3 to 3.0.

Additives can be incorporated into the layer having a neutralizing function of the present invention for various purposes. For example, hardening agents well known to those skilled in the art for hardening this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. for improving the brittleness of the film can be added. Other as needed
Antioxidants, development inhibitors and their precursors can also be added.

(E) Neutralization Timing Layer The timing layer used in combination with the neutralization layer is, for example, gelatin, polyvinyl alcohol, a partial acetalization product of polyvinyl alcohol, cellulose acetate, or partially hydrolyzed polyvinyl acetate. Polymers that lower the alkali permeability; latex polymers that are made by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid monomers to increase the activation energy of alkali permeation; polymers that have a lactone ring are useful. ..

Among them, JP-A-54-136328,
U.S. Pat. Nos. 4,267,262 and 4,009,03
No. 0, No. 4,029,849, and other timing layers using cellulose acetate; JP-A-54-12
No. 8335, No. 56-69629, No. 57-6843.
U.S. Pat. Nos. 4,056,394 and 4,061,
No. 496, No. 4,199,362, No. 4,250,2
No. 43, No. 4,256,827, No. 4,268,60
Latex polymers made by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid disclosed in US Pat. No. 4, etc .; Polymers having a lactone ring disclosed in US Pat. No. 4,229,516; 56-2573
5, No. 56-97346, No. 57-6842, European Patent (EP) No. 31,957A1, No. 37,
The polymers disclosed in 724A1 and 48,412A1 are particularly useful.

In addition, the materials described in the following documents can also be used. U.S. Pat. Nos. 3,412,893 and 3,45
5,686, 3,575,701 and 3,77
8,265, 3,785,815, 3,84
7,615, 4,088,493, 4,12
3,275, 4,148,653, 4,20
1,587, 4,288,523, 4,29
No. 7,431, West German patent application (OLS) 1,622,9
No. 36, No. 2, 162, 277, Research
Disclosure 15162 No. 151 (1
976).

JP-A-59-202463, US Pat. Nos. 4,297,431, 4,288,523, 4,201,587, 4,229,516 and 55- No. 121438, No. 56-166212, No. 55-41490, No. 55-54341, No. 56-.
102852, 57-141644, 57-1
No. 73834, No. 57-179841, West German Patent Application Publication (OLS) 2,910,271, European Patent Application Publication No. 31,957A1, Research Disc.
loss No. 18452 etc. can be mentioned.

The neutralization timing layer may be a single layer or multiple layers. In addition, the timing layer made of these materials,
For example, U.S. Pat. No. 4,009,029, West German patent application (OLS) 2,913,164, and 3,014,67.
No. 2, JP-A Nos. 54-155837 and 55-1387.
45 and the like, development inhibitors and / or their precursors, and US Pat. No. 4,201,5
Hydroquinone precursor disclosed in No. 78,
It is also possible to incorporate other useful additives for photography or their precursors.

(F) Peeling Layer In the invention, a peeling layer is provided for peeling off the image-receiving element of the photosensitive element after processing, if necessary. Therefore, this release layer must be easy to remove after the treatment. As a material for this, for example, JP-A-47-8237
No. 59-220727, 59-229555.
No. 49-4653, U.S. Pat. No. 3,220,83.
5, 4,359,518, JP-A-49-4334.
No. 56-65133, No. 45-24075, U.S. Pat. No. 3,227,550, No. 2,759,825.
Nos. 4,401,746, 4,366,227 and the like can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. For example, 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, and gum arabic. Also, various modified gelatins such as acetylated gelatin and phthalated gelatin can be used. Yet another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol,
It is polyacrylate, polymethylmethacrylate, polybutylmethacrylate, or a copolymer thereof.

The release layer may be a single layer or may be composed of a plurality of layers as described in JP-A-59-220727 and JP-A-60-60642.

(G) Binder A hydrophilic binder is preferably used as the binder of the constituent layers of the photosensitive element and the image receiving element. As an example thereof, Japanese Patent Laid-Open No. 62-62
The compounds described on pages (26) to (28) of No. 253159 can be mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran and pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Also, JP-A-62-245
Superabsorbent polymer described in No. 260 or the like, that is, -CO
OM or -SO ₃ M (M is a hydrogen atom or an alkali metal) copolymer of homopolymer or a vinyl monomer together or with other vinyl monomers of the vinyl monomer having a (e.g. sodium methacrylate, ammonium methacrylate, Sumitomo Chemical (Sumikagel L-5H manufactured by Co., Ltd.)
Also used. These binders can be used in combination of two or more.

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

The constituent layers (including the back layer) of the light-sensitive element or the image-receiving element include dimensional stabilization, curl prevention, adhesion prevention,
Various polymer latices may be incorporated for the purpose of improving physical properties of the film such as prevention of cracking of the film and prevention of pressure increase / decrease. Specifically, JP-A Nos. 62-245258 and 62-62
Any of the polymer latexes described in JP-A-136648 and JP-A-62-10066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, cracking of the image receiving layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, a curl preventing effect is obtained. can get.

(H) Hardener As the hardener used in the constituent layers of the photosensitive element and the image receiving element,
U.S. Pat. No. 4,678,739, column 41, JP-A-59
-116655, 62-245261, 61-
Examples include hardeners described in 18942 and the like. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners (compounds of the following chemical formula 22), vinyl sulfone type hardeners (N,
N'-ethylene-bis (vinylsulfonylacetamide)
Ethane, etc.), N-methylol type hardener (such as dimethylol urea), or polymer hardener (JP-A-62-23).
4157 and the like).

(I) Others In the constituent layers of the light-sensitive element and the image-receiving element, various surfactants can be used for the purposes of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. .. Specific examples of the surfactant are disclosed in JP-A-62-173463 and JP-A-62-1834.
No. 57 etc.

The constituent layers of the light-sensitive element and the image-receiving element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving releasability. Typical examples of organic fluoro compounds include fluorine-containing surfactants described in JP-B No. 57-9053, columns 8 to 17, JP-A Nos. 61-20944 and 62-135826, and fluorine oils. And the hydrophobic fluorine compound such as solid fluorine compound resin such as oily fluorine compound or tetrafluoroethylene resin.

A matting agent can be used in the light-sensitive element and the image-receiving element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
88256 (29) page, benzoguanamine resin beads, polycarbonate resin beads, A
Japanese Patent Laid-Open Nos. 63-274944 and 63-4, such as S resin beads.
There are compounds described in 3-274952.

In addition, the constituent layers of the light-sensitive element and the image-receiving element may contain an antifoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are disclosed in JP-A-61-1
88256 et al. (26)-(32).

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the image-receiving element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. From the physicochemical function, such as base or base precursor, nucleophilic compound, high boiling organic solvent (oil), surfactant, silver or silver ion It is classified as a compound that interacts with. However, these substance groups generally have a composite function, and usually have some of the above-mentioned promoting effects together. For details of these, see US Pat. No. 4,6.
No. 78,739, columns 38-40.

(J) Processing Composition The processing composition used in the present invention is one which is uniformly spread on the photosensitive element after the exposure of the photosensitive element, and the photosensitive layer is developed by the components contained therein. Therefore, in the composition, deterioration of alkali, thickener, light-shielding agent, electron transfer agent (developer), and further development accelerator, development inhibitor and developer for controlling development is prevented. It contains an antioxidant and the like. If necessary, the composition may contain a light-shielding agent.

Alkali is sufficient to adjust the pH of the liquid to 12 to 14, and alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide, lithium hydroxide),
Examples thereof include alkali metal phosphates (for example, potassium phosphate), guanidines, and quaternary amine hydroxides (for example, tetramethylammonium hydroxide). Of these, potassium hydroxide and sodium hydroxide are preferable.

The thickening agent is used to spread the treatment liquid uniformly.
It is also necessary in order to maintain close contact between the light-sensitive element and the image-receiving element during development and to prevent the processing liquid component from remaining on the surface of the image-receiving element during peeling.

For example, an alkali metal salt of polyvinyl alcohol, hydroxyethyl cellulose or carboxymethyl cellulose is used, preferably hydroxyethyl cellulose or sodium carboxymethyl cellulose.

When the image-receiving element is a transparent support and does not have a light-shielding function, a light-shielding agent can be contained.
As the light-shielding agent, either a dye or a pigment, or a combination thereof can be used as long as it does not diffuse to the dye image-receiving layer to generate stain. Carbon black is a typical example, but a combination of titanium white and a dye may also be used. The dye may be a temporary light-shielding dye that becomes colorless after a certain time of treatment.

As the preferable electron transfer agent, any electron transfer agent can be used as long as it cross-oxidizes the electron donor and does not substantially produce stain even when oxidized. Such electron transfer agents may be used alone or in combination of two or more kinds, and may be used in a precursor type. Specific examples of these electron transfer agents include aminophenols and pyrazolidinones. Of these, pyrazolidinones are particularly preferable because they produce 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.

The above treatment composition is described in US Pat.
3,181, 2,643,886, 2,65
No. 3,732, No. 2,723,051, No. 3,05
6,491, 3,056,492, 3,15
It is preferable to fill and use a container that can be ruptured by pressure as described in No. 2,515.

(K) Structure of Light-Sensitive Material A color diffusion transfer instant light-sensitive material can be formed by combining the above elements.

The color diffusion transfer instant film unit is 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 different supports, and after exposure to an image, the photosensitive layer is exposed. The element and the dye image receiving element are superposed, the processing composition is developed therebetween, and the dye image receiving element is peeled off to obtain a dye image transferred to the dye image receiving layer.

On the other hand, in the peeling-free type, a dye image-receiving layer and a photosensitive layer are coated between a transparent support and the other support, but the image-receiving layer and the photosensitive layer are the same transparent support. There are a form applied and a form applied on another support.

In the former case, a white reflective layer is coated between the image receiving layer and the photosensitive layer, and in the latter case, the processing composition developed between the image receiving layer and the silver halide emulsion layer is used. By containing a white pigment, the dye image transferred to the image receiving layer can be observed with reflected light.

In the peeling type, the image-receiving element and the light-sensitive element are generally attached to different supports, and in addition to the dye-image-receiving layer as an image-receiving material, a layer having a neutralizing function, a neutralizing timing layer, and a peeling layer if necessary. Is provided. As the support of the image receiving material,
It is preferable to use a white support having a light shielding function. On the other hand, the photosensitive material is provided with a layer having a neutralizing function and a neutralization timing layer, if necessary, in addition to the photosensitive layer. As the support of the photosensitive material, it is preferable to use a black support having a light shielding function. Regarding the film unit, JP-A-61
The thing described in No. 47956 can be applied.

Further, as a peeling type, Japanese Patent Laid-Open No. 1987/1987.
As described in Japanese Patent Application No. 47 and Japanese Patent Application No. 1-68749, a film unit in which a dye image-receiving layer / a release layer / a photosensitive layer are attached to the same support in this order can be applied.

The release-free type is a cover sheet material in which a layer having a neutralizing function and a neutralization timing layer are provided on another transparent support when the photosensitive layer and the image receiving layer are provided on the same support. Is used. Regarding the film unit, those described in JP-B-46-16356 and JP-A-50-13040 can be applied.

[0223]

EXAMPLES The present invention will be specifically described below 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. Preparation of emulsion-EM1 (tabular silver bromide grains): 0.05M
To 1 liter of a 0.8% by weight gelatin aqueous solution containing potassium bromide, 0.40 M silver nitrate aqueous solution and 0.15 M potassium bromide aqueous solution are added in an amount of 30 cc with stirring by a double jet method. .. During this period, the gelatin aqueous solution was kept at 30 ° C. After the addition, the temperature was raised to 75 ° C. Further, after the completion of the above first-stage addition in which 30 g of gelatin was added after the addition, 90 cc of 0.4 M silver nitrate aqueous solution was added.

Further, after that, 176 g of silver nitrate was accelerated in 65 minutes (the flow rate at the end was 2 times the flow rate at the start).
1 ×). During this period, pBr was kept at 2.40. The particles thus formed (hereinafter referred to as seed crystals) were washed by a conventional flocculation method, and gelatin was added thereto, followed by addition of gelatin at pH 6.5 and pAg 8.0 at 40 ° C.
I adjusted it to be.

The seed crystal emulsion thus prepared is Emulsion 1
It contained 203 g of silver halide per kg. The seed crystal was dissolved in 3.7 liter of an aqueous solution containing 0.8% by weight of gelatin, and the temperature was kept at 75 ° C. and pBr 1.60. After this, 107 g of silver nitrate was added while keeping pBr at 1.60.

Further, after adding ammonium thiocyanate, silver nitrate was added so that pBr would be 2.70. Then, the emulsion was cooled to 35 ° C., washed by a conventional flocculation method, added with gelatin, adjusted to pH 6.5 and pAg 8.5 at 40 ° C., and then stored in a cool dark place. The tabular grains had an average projected area circle-equivalent diameter of 1.3 μm and an average thickness of 0.25 μm. This emulsion also contained 213 g of silver halide per kg of emulsion.

Preparation of Emulsion-EM2 (cubic silver chlorobromide grains): 25 g of lime-processed gelatin was added to 800 ml of distilled water, dissolved at 40 ° C., and the pH was adjusted to 3.8 with sulfuric acid. An aqueous solution (I) was prepared by further dissolving 1.7 g of sodium chloride and 0.01 g of N, N'-dimethylethylthiourea in this aqueous solution. Next, 125g of silver nitrate
Was dissolved in 500 ml of distilled water to give an aqueous solution (II). Furthermore, sodium chloride 43g and yellow blood salt 0.3m
g and 0.01 mg of iridium dichloride dipotassium salt were dissolved in distilled water to give an aqueous solution (III). 60
The aqueous solution (II) and the aqueous solution (III) were simultaneously added and mixed into the aqueous solution (I) kept at 0 ° C. for 45 minutes. After removing excess salts from the dispersion of silver halide grains obtained by the above operation by the coagulation sedimentation method,
Add 50 g of lime-processed gelatin and disperse again to prepare emulsion EM2.
Was prepared.

Emulsion for red light-sensitive layer-A1, B1, C1, D
Preparation of 1, E1, F1, and G1: Preparation of A1 The temperature of the emulsion EM1 was set to 60 ° C., the sensitizing dyes S-1 and S-2 below were added, and after 10 minutes, Na ₂ S ₂ O ₃ was added to 1 mol of silver. 5 × 10 ⁻⁶ mol per unit, and ammonium thiocyanate and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached, the temperature was lowered to end the chemical sensitization,
Emulsion A1 was prepared. The sensitizing dyes S-1 and S-2, ammonium thiocyanate and KAuCl ₄ were added in such amounts that maximum sensitivity was obtained.

Preparation of B1 Sensitizing dyes S-1 and S-2 shown below were added to emulsion EM2 at a temperature of 60 ° C., and 10 minutes later, Na ₂ S ₂ O ₃ was added at 2.5 × 10 ⁻ per mol of silver. ⁶ mol, and ammonium thiocyanate and KAuCl ₄ were added for chemical aging,
When the maximum sensitivity was reached, the temperature was lowered to terminate the chemical sensitization, and Emulsion B1 was prepared. Sensitizing dyes S-1 and S-2,
The amounts of ammonium thiocyanate and KAuCl ₄ added were selected such that the highest sensitivity was obtained.

Preparation of C1 The following sensitizing dyes S-1 and S-2 were added to the emulsion EM1 at a temperature of 60 ° C., and after 10 minutes, Na ₂ S ₂ O ₃ was added in an amount of 2 × 10 ^-6 mol per mol of silver. Of the selenium sensitizer represented by [Chemical Formula 7] -21, and 2 × 10 ^-6 mol per mol of silver, and ammonium thiocyanate salt and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached. The temperature was lowered to terminate the chemical sensitization, and Emulsion C1 was prepared. Sensitizing dye S-
1 and S-2, ammonium thiocyanate and KAuC
The amount of l ₄ added was selected so that the highest sensitivity was obtained.

Preparation of D1 The following sensitizing dyes S-1 and S-2 were added to the emulsion EM1 at a temperature of 60 ° C., and after 10 minutes, a selenium sensitizer represented by [Chemical Formula 7] -21 was added to 1 mol of silver. Then, 2 × 10 ^-6 mol per mol, ammonium thiocyanate salt and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached, the temperature was lowered to terminate the chemical sensitization to prepare Emulsion D1. Sensitizing dyes S-1 and S-2, ammonium thiocyanate and KA
The amount of uCl ₄ added was selected so that the highest sensitivity was obtained.

Preparation of E1 Emulsion EM1 was heated to 60 ° C., sensitizing dyes S-1 and S-2 below were added, and after 10 minutes, a selenium sensitizer represented by [Chemical Formula 3] -1 was added to 1 mol of silver. Then, 2 × 10 ^-6 mol per mol, ammonium thiocyanate salt and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached, the temperature was lowered to terminate the chemical sensitization to prepare Emulsion E1. Sensitizing dye S
-1, S-2, ammonium thiocyanate and KAu
The amount of Cl ₄ added was selected so that the highest sensitivity was obtained.

Preparation of F1 The following sensitizing dyes S-1 and S-2 were added to the emulsion EM2 at a temperature of 60 ° C., and 10 minutes later, Na ₂ S ₂ O ₃ was added in an amount of 1 × 10 ^-6 mol per mol of silver. Of the selenium sensitizer represented by [Chemical Formula 7] -21, and 1 × 10 ^-6 mol per mol of silver, and ammonium thiocyanate and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached. The temperature was lowered to terminate the chemical sensitization, and Emulsion F1 was prepared. Sensitizing dye S-
1 and S-2, ammonium thiocyanate and KAuC
The amount of l ₄ added was selected so that the highest sensitivity was obtained.

Preparation of G1 The following sensitizing dyes S-1 and S-2 were added to Emulsion EM2 at a temperature of 60 ° C., and after 10 minutes, 1 mol of selenium sensitizer represented by [Chemical Formula 7] -21 was added to silver. 1 × 10 ^-6 mol per mol, and ammonium thiocyanate and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached, the temperature was lowered to terminate the chemical sensitization, and Emulsion G1 was prepared. Sensitizing dyes S-1 and S-2, ammonium thiocyanate and KA
The amount of uCl ₄ added was selected so that the highest sensitivity was obtained.

Preparation of H1 The following sensitizing dyes S-1 and S-2 were added to the emulsion EM2 at a temperature of 60 ° C., and after 10 minutes, a selenium sensitizer represented by [Chemical Formula 7] -21 was added to 1 mol of silver. Then, 2 × 10 ^-6 mol per mol, ammonium thiocyanate salt and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached, the temperature was lowered to terminate the chemical sensitization to prepare Emulsion G1. Sensitizing dyes S-1 and S-2, ammonium thiocyanate and KA
The amount of uCl ₄ added was selected so that the highest sensitivity was obtained.

Emulsion for green photosensitive layer-A2, B2, C2, D
Preparation of 2, E2, F2, G2, H2: Sensitizing dye
-Emulsion for red photosensitive layer-A1, B1, except for changing to -3
In the same manner as in the preparation of C1, D1, E1, F1, G1 and H1, emulsions for green photosensitive layers-A2, B2, C2, D2, E2,
F2, G2 and H2 were prepared.

Emulsion for blue photosensitive layer-A3, B3, C3, D
Preparation of 3, E3, F3, G3 and H3: Sensitizing dye
-Emulsion for red photosensitive layer-A1, B1, except for changing to -4
Emulsion for green photosensitive layer-A3, B3, C3, D3, E3, similar to the preparation of C1, D1, E1, F1, G1, and H1.
F3, G3 and H3 were prepared.

The emulsion thus obtained is shown in Table 1.

[0239]

[Chemical 32]

[0240]

[Chemical 33]

[0241]

[Chemical 34]

[0242]

[Table 1]

[0243]

[Table 2]

Next, a method for preparing a gelatin dispersion of the dye-donor compound will be described. Yellow dye-donor compound (1)
Weigh 18 g ^* , high boiling organic solvent (1) ^* 12 g,
Add 51 ml of ethyl acetate and heat to dissolve at about 60 ° C.
A uniform solution was obtained. 10 of this solution and lime-processed gelatin
% Aqueous solution (100 g), water (60 cc) and sodium dodecylbenzenesulfonate (1.5 g) were mixed with stirring and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a yellow dye-donor compound dispersion.

Dispersions of magenta and cyan dye-donor compounds were made using the magenta dye-donor compound (2) ^* or cyan dye-donor compound (3) ^* , as well as the yellow dye-donor compound.

Next, a method for preparing a gelatin dispersion of an electron donor will be described. 20.6 g of the electron donor (1) ^* and 13.1 g of the high boiling point organic solvent (1) ^* were weighed, 120 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. 10% aqueous solution of this solution and lime-processed gelatin 1
After stirring and mixing 00 g, 60 cc of water and 1.5 g of sodium dodecylbenzenesulfonate, the mixture was dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a dispersion of electron donors.

Next, a method for preparing a gelatin dispersion of the diffusion resistant reducing agent for the intermediate layer will be described. Diffusion resistant reducing agent (1)
^* 23.5 g and the high boiling point organic solvent (1) ^* 8.5 g were dissolved in 120 ml of ethyl acetate at about 60 ° C. to obtain a uniform solution. This solution and 100% 10% aqueous solution of lime-processed gelatin
g, 15 ml of a 5% aqueous solution of the surfactant (3) ^* , and 0.2 g of dodecylbenzenesulfonic acid were stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a dispersion of the diffusion resistant reducing agent for the intermediate layer.

From these, comparative photosensitive element 101 having the constitution shown in Table 2 below was prepared.

[0249]

[Table 3]

[0250]

[Table 4]

[0251]

[Table 5]

The compounds shown in Table 2 used in this photosensitive element are shown below.

[0253]

[Chemical 35]

[0254]

[Chemical 36]

[0255]

[Chemical 37]

[0256]

[Chemical 38]

The image receiving element was prepared as follows. Paper support resistance: 150 μm thick paper laminated with polyethylene of 30 μm on each side. To the polyethylene on the image receiving layer side, 10% by weight of titanium oxide is dispersed and added to polyethylene. Back side: (a) Carbon black 4.0 g / m ² , gelatin 2.
Light-shielding layer of 0 g / m ² . (B) Titanium oxide 8.0 g / m ² , gelatin 1.0 g /
m ² white layer. (C) Protective layer of gelatin 0.6 g / m ² .

The coating is carried out in the order of (a) to (c), and the film is hardened with a hardener. Image-receiving layer side: (1) A neutralizing layer containing 22 g / m ^{2 of} an acrylic acid-butyl acrylate (molar ratio 8: 2) copolymer having an average molecular weight of 50,000. (2) Cellulose acetate having an oxidation degree of 51.3% (the weight of acetic acid released by hydrolysis is 0.513 g per 1 g of the sample), and styrene-maleic anhydride having an average molecular weight of about 10,000 (molar ratio 1 1) A second timing layer containing 4.5 g / m ^{2 of} copolymer in a weight ratio of 95: 5. (3) An intermediate layer containing 0.4 g / m ^{2 of} poly-2-hydroxyethyl methacrylate. (4) Styrene / butyl acrylate / acrylic acid / N
A methylol acrylamide in a weight ratio of 49.7 / 42.
The polymer latex emulsion-polymerized by 3/4/4 and the polymer latex emulsion-polymerized by methylmethacrylate / acrylic acid / N-methylol acrylamide at a weight ratio of 933/4 have a solid content ratio of 6: 4. A first timing layer that is blended and contains 1.6 g / m ^{2 of} total solids. (5) 3.0 g of a polymer mordant having a repeating unit of the following chemical formula 40 using the compound of the following chemical formula 39 as a coating aid
An image receiving layer coated with m ² and 3.0 g / m ² of gelatin.

[0259]

[Chemical Formula 39]

[0260]

[Chemical 40]

(6) A protective layer coated with 0.6 g / m ² of gelatin. The above (1) to (6) are applied in this order and hardened with a hardener.

The formulation of the treatment liquid is shown below. A destructible container was filled with 0.8 g of the treatment liquid having the following composition. 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10.0 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 4.0 g potassium sulfite (anhydrous) 4.0 g hydroxy Ethyl cellulose 40 g Potassium hydroxide 64 g Benzyl alcohol 2.0 g Water was added to bring the total amount to 1 kg.

Next, the emulsions of the second, sixth and tenth layers are shown in Table 3 as emulsions B1 to B3, C1 to C3 and D1 to D.
3, E1-E3, F1-F3, G1-G3, H1-H3
Was changed to Samples 102 to 108.

[0264]

[Table 6]

After exposing the light-sensitive elements 101 to 108 from the emulsion layer side through a gray continuous tone wedge,
The image receiving layer side of the image receiving element was superposed and the processing solution was spread between both materials so as to have a thickness of 60 μm with the aid of a pressure roller. The processing was carried out at 25 ° C., and after 1.5 minutes, the light-sensitive material and the image-receiving element were peeled off.

The reflection density transferred to each image receiving element was measured with a color densitometer. The results are shown in Table-4.

[0267]

[Table 7]

(Example 2) Instead of the selenium sensitizers represented by [Chemical formula 3] -1 and [Chemical formula 7] -21 used in Example 1, [Chemical formula 3] -2, 4, 8, 14 , 19, [Chemical 7]
Similar experiments were carried out using -22, 26, 29, 39 or colloidal metal selenium, and almost the same results as in Example 1 were obtained.

[0269]

According to the present invention, it was found that an excellent image having high sensitivity and low minimum density can be obtained.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 24, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

Of these selenium compounds, compounds represented by the following general formulas ( II ) and ( II ) are preferable. General formula ( II )

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

In the general formula ( II ), preferably Z ₁ represents an alkyl group, an aryl group or —NR ₁ (R ₂ ), and Z 1
₂ represents -NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

In the general formula ( II ), more preferably N, N
-Dialkylselenourea, N, NN, -trialkyl-
N'-acyl selenoureas, tetraalkyl selenoureas,
Represents N, N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

General formula ( III )

[Procedure Amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

In the general formula ( III ), Z ₃ , Z ₄ ,
The aliphatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group or an aralkyl group (for example, methyl group, ethyl group). Group, n-propyl group, isopropyl group, t
-Butyl group, n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group , Benzyl group, phenethyl group).

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

In the general formula ( III ), Z ₃ , Z ₄ ,
The aromatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed ring aryl group (for example, a phenyl group, a pentafluorophenyl group, a 4-chlorophenyl group, 3 -Sulfophenyl group, α-naphthyl group, 4-
Represents a methylphenyl group).

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

In the general formula ( III ), Z ₃ , Z ₄ ,
The heterocyclic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Represents a heterocyclic group (eg, pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group).

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

In the general formula ( III ), R ₇ , R ₁₀
The cation represented by R ₁₁ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

In the general formula ( III ), preferably Z ₃ and Z
₄ or _{Z 5} is an aliphatic group, an aromatic group or represents -OR _{7, R 7} represents an aliphatic group or an aromatic group. In formula ( III ), trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate is more preferred.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0033

[Correction method] Change

[Correction content]

Specific examples of the compounds represented by formulas ( II ) and ( III ) are shown below, but the invention is not limited thereto.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

Regarding the selenium sensitization method, US Pat.
No. 74944, No. 1602592, No. 16234
No. 99, No. 3297446, No. 3297447
No. 3320069, No. 3408196, No. 3408197, No. 3442653, No. 34.
No. 20670, No. 3591385, French Patent No. 2693038, No. 2093209, Japanese Patent Publication No. 52
-34491, 52-34492, and 53-29.
5, 57-22090, and JP-A-59-18053.
No. 6, No. 59-185330, No. 59-181337.
No. 59-187338 and No. 59-192241.
Issue No. 60-150046, Issue No. 60-151637
No. 61-246738, JP-A-3-42221,
Japanese Patent Application Nos. 1-287380, 1-250950, 1-254441, 2-334090 and 2-11
No. 0558, No. 2-130976, No. 2-13918
No. 3, No. 2-229300, and British Patent No. 255.
No. 846, No. 861984, and H.M. E. SPe n
cer et al., Journal of Photogra
phic Science Magazine, Volume 31, 158-169
Page (1983) and the like.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Name of item to be corrected] 0066

[Correction method] Change

[Correction content]

The grain thickness is less than 1.0 μm, preferably 0.05 to 0.5 μm, more preferably 0.08 to
It is 0.3 μm.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction content]

[0069] In its us in tabular grains may be a silver halide having a different composition by an epitaxial junction are joined, also for example silver thiocyanate, it may be joined with compounds other than silver halide such as silver oxide .. These emulsion grains are described in U.S. Pat.
142,900, 4,459,353, British Patent 2,038,792, U.S. Patent 4,349,62.
No. 2, No. 4,395,478, No. 4,433,501
No. 4,463,087, No. 3,656,962
No. 3,852,067, JP-A-59-16254.
No. 0 and the like.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0141

[Correction method] Change

[Correction content]

(2) Electron Donor In the present invention, an electron donor (when referred to as an electron donor in the present invention, a precursor thereof is used), the details of these compounds are described in US Pat. No. 4,783, 396
No., European Patent Publication No. 220,746A2, Public Technical Report 87
No. 6199 and the like. A particularly preferable electron donor is a compound represented by the following general formula ( B ) or ( C ).

[Procedure 16]

[Document name to be amended] Statement

[Name of item to be corrected] 0146

[Correction method] Change

[Correction content]

R ²⁰¹ , R ²⁰² , R ²⁰³ and R
²⁰⁴ is a hydrogen atom, an alkyl group, an aryl group,
An alkylthio group, an arylthio group, a sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, scan Le <br/> Famoiru group, an amide group, an imide group, a carboxyl group,
Represents a sulfonamide group and the like. These groups may have a substituent if possible.

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0147

[Correction method] Change

[Correction content]

However, the total number of carbon atoms of R ^{201 to} R ²⁰⁴ is 8 or more. Further, in the general formula ( B ), R
²⁰¹ and R ²⁰² and / or R ²⁰³ and R
²⁰⁴ is R ²⁰¹ and R ²⁰² , R ²⁰² and R ²⁰³ and / or R ^{203 in} the general formula ( C ) ^.
And R ²⁰⁴ may combine with each other to form a saturated or unsaturated ring.

[Procedure 18]

[Document name to be amended] Statement

[Correction target item name] 0148

[Correction method] Change

[Correction content]

Among the electron donors represented by the general formula ( B ) or ( C ), those in which at least two of R ^{201 to} R ²⁰⁴ are substituents other than hydrogen atom are preferable.
Particularly preferred compounds are those in which at least one of R ²⁰¹ and R ²⁰² and at least one of R ²⁰³ and R ²⁰⁴ are a substituent other than a hydrogen atom.

[Procedure Amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0201

[Correction method] Change

[Correction content]

The constituent layers (including the back layer) of the light-sensitive element or the image-receiving element include dimensional stabilization, curl prevention, adhesion prevention,
Various polymer latexes may be contained for the purpose of improving the physical properties of the film such as prevention of cracking of the film and prevention of pressure increase / decrease. Specifically, JP-A Nos. 62-245258 and 62-62
Any of the polymer latexes described in JP-A-136648 and JP-A-62-10066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, cracking of the image receiving layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, a curl preventing effect is obtained. can get.

[Procedure amendment 20]

[Document name to be amended] Statement

[Correction target item name] 0202

[Correction method] Change

[Correction content]

(H) Hardener As the hardener used in the constituent layers of the photosensitive element and the image receiving element,
U.S. Pat. No. 4,678,739, column 41, JP-A-59
-116655, 62-245261, 61-
Examples include hardeners described in 18942 and the like. More specifically, aldehyde type hardener (formaldehyde etc.), aziridine type hardener, epoxy type hardener , vinyl sulfone type hardener (N, N'-ethylene-bis (vinylsulfonylacetamide) ethane Etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (compounds described in JP-A-62-234157).

[Procedure correction 21]

[Document name to be amended] Statement

[Name of item to be corrected] 0227

[Correction method] Change

[Correction content]

Preparation of emulsion-EM2 (silver bromide cubic grains): First, solutions I to III shown in Table-A were prepared, and emulsions EM2 were prepared as follows. For liquid I, as shown in Table-B, the first stage and the second stage
Solution II and I while maintaining pAg at 7.1
Solution II was added by the double jet method. After the addition was completed, the emulsion was cooled to 35 ° C., washed by a conventional flocculation method, added with 50 g of bone gelatin, adjusted to pH 6.6 and pAg 8.5 at 40 ° C., and then stored in a cool dark place.

[Procedure correction 22]

[Document name to be amended] Statement

[Name of item to be corrected] 0142

[Correction method] Change

[Correction content]

[0142]

[Chemical formula 26] ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 8, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0231

[Correction method] Change

[Correction content]

Preparation of D1 The following sensitizing dyes S-1 and S-2 were added to the emulsion EM1 at a temperature of 60 ° C., and after 10 minutes, a selenium sensitizer represented by [Chemical Formula 7] -21 was added to 1 mol of silver. 3.3 x 10 ^-6 mol per
Further, ammonium thiocyanate and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached, the temperature was lowered to terminate the chemical sensitization to prepare Emulsion D1. The sensitizing dyes S-1 and S-2, ammonium thiocyanate and KAuCl ₄ were added in such amounts that maximum sensitivity was obtained.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0232

[Correction method] Change

[Correction content]

Preparation of E1 Emulsion EM1 was heated to 60 ° C., sensitizing dyes S-1 and S-2 below were added, and after 10 minutes, a selenium sensitizer represented by [Chemical Formula 3] -1 was added to 1 mol of silver. 3.3 × 10 ^-6 mol per mol, and ammonium thiocyanate salt and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached, the temperature was lowered to terminate the chemical sensitization, and Emulsion E1 was prepared. .. Sensitizing dyes S-1 and S-2, ammonium thiocyanate and K
The amount of AuCl ₄ added was selected so that the highest sensitivity was obtained.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0234

[Correction method] Change

[Correction content]

Preparation of G1 The following sensitizing dyes S-1 and S-2 were added to Emulsion EM2 at a temperature of 60 ° C., and after 10 minutes, 1 mol of selenium sensitizer represented by [Chemical Formula 7] -21 was added to silver. 1.7 × 10 ^-6 mol per
Further, ammonium thiocyanate and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached, the temperature was lowered to terminate the chemical sensitization to prepare Emulsion G1. The sensitizing dyes S-1 and S-2, ammonium thiocyanate and KAuCl ₄ were added in such amounts that maximum sensitivity was obtained.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0235

[Correction method] Change

[Correction content]

Preparation of H1 Emulsion EM2 was heated to 60 ° C., sensitizing dyes S-1 and S-2 shown below were added, and after 10 minutes, a selenium sensitizer represented by [Chemical Formula 7] -21 was added to 1 mol of silver. 3.3 x 10 ^-6 mol per
Further, ammonium thiocyanate and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached, the temperature was lowered to terminate the chemical sensitization to prepare Emulsion G1. The sensitizing dyes S-1 and S-2, ammonium thiocyanate and KAuCl ₄ were added in such amounts that maximum sensitivity was obtained.

Claims (1)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer in combination with a dye image-forming substance and an electron donor, wherein the dye image-forming substance is represented by the following general formula (I). A silver halide emulsion grain comprising at least one reducible dye-providing compound that releases a diffusible dye when reduced and contained in at least one emulsion layer of the silver halide emulsion layer. A color diffusion transfer light-sensitive material characterized by being chemically sensitized by an agent. General formula (I) PWR- (Time) _t -Dye In the formula, PWR is reduced to give-(Tim).
e) represents a group releasing _t- Dye, and Time is PWR
Represents a group which is released as-(Time) _t -Dye and then releases Dye through a subsequent reaction, and t is 0.
Alternatively, it represents an integer of 1, and Dye represents a dye or a precursor thereof.