JP2000250182A - Method for formation of color diffusion transfer photographic image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a method for the formation of color transfer diffusion photographic images which does not produce stains after peeling in a peel-apart method by using an alkaline treating compsn. containing at least one kind of specified compd. to treat a photosensitive element. SOLUTION: In the method for the formation of color transfer diffusion photographic images, a photosensitive element is treated by using an alkaline treating compsn. containing at least one kind of compd. expressed by the formula. In the formula, R is a hydrogen atom, unsubstd. alkyl group or -L2-A2, each of L1 and L2 is an alkylene group, each of A1 and A2 is a carboxyl group, sulfo group, phosphono group, phosphinate group or its salt, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylamino group, sulfamoyl group, sulfonylamino group, alkylthio group, cyano group, ureido group or ammonio group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color diffusion transfer photographic image forming method, and more particularly, to a method in which an alkaline processing composition is developed between a photosensitive element and an image receiving element, the image receiving element is peeled off and transferred to an image receiving layer. A color diffusion transfer photographic image forming method for obtaining a dye image, and a color diffusion transfer photographic image forming by a mono-sheet method in which an alkaline processing composition is developed between a photosensitive element and a cover sheet and an image is obtained in a unit without peeling off More particularly, the present invention relates to a color diffusion transfer photographic image forming method in which a transferred image has less stain.

[0002]

2. Description of the Related Art An alkaline thickener is developed and developed on a photosensitive element in which an image receiving element and a photosensitive element are integrated, and an azo dye having a diffusibility different from that of the azo dye image forming substance itself is given. A color diffusion transfer photographic image forming method using an azo dye image forming substance has been well known in the art. For example, as shown in JP-B-49-26896, an alkaline thickening liquid is developed between an image receiving element and a photosensitive element, and after development and transfer, the image receiving element is peeled off to obtain a dye image transferred to an image receiving layer. An image forming method by a peel apartment method is well known. Further, an image forming method using a mono-sheet system in which an alkaline processing composition is spread between a photosensitive element and a cover sheet and a transfer image is obtained as a unit without peeling is also well known.

As a dye image forming substance used in these transfer systems, a dye donating substance described in US Pat. No. 3,928,312 is known. In order to immobilize the released anionic dye, U.S. Pat. Nos. 3,958,995;
It is known that a quaternary ammonium salt polymer is used as a mordant, as described in 8,088 and the like. Further, in order to improve the light fastness of the immobilized dye, side chains described in U.S. Pat. Nos. 4,115,124, 4,282,305 and 4,273,853 are disclosed. Polymers having a tertiary imidazole ring are known. Further, in order to enhance the mordant property of the dye and the stability to light, tertiary imidazole copolymers described in JP-B-4-17418 and JP-A-60-60643 are disclosed. And copolymers having a quaternary ammonium salt group and a tertiary imidazole group described in the above publication. In addition, it is known to use a polymer having a pyridine ring in a side chain as a mordant.

In these color diffusion transfer photographic image forming methods, in the case of the peel-apart method, when the image receiving element is peeled off after the alkaline thickening solution is developed, a yellow to pink stain is generated in the image.
In the case of the mono-sheet system, there is a problem that the yellow stain is increased. In order to improve these stains, JP-A-59-58428 and JP-A-2-25195 have been proposed.
No. 4 proposes a method of developing in the presence of a sulfinic acid or a salt thereof, but it does not reach the point of completely preventing stain. Also, JP-A-4-7364
No. 8 describes a method of adding a specific non-diffusible hydroxylamine derivative to an image receiving element. However, since the cause of stain is caused by oxidation of a developing agent in a processing solution,
Again, stain could not be completely prevented, and better means of improvement were desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color diffusion transfer photographic image forming method which does not generate stain after peeling by a peel-apart method. Another object of the present invention is to provide a color diffusion transfer photographic image forming method having a low stain by a monosheet method.

[0006]

The object of the present invention has been attained by the following (1) to (3). (1) A color diffusion transfer photographic image forming method for processing a photosensitive element using an alkaline processing composition, comprising at least one compound represented by the following general formula (I).

[0007]

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(In the formula (I), R represents a hydrogen atom, an unsubstituted alkyl group, an unsubstituted alkenyl group, or -L ² -A ^2. L ¹ and L ² each represent an alkylene group.
¹ and A ² are a carboxyl group (acid or salt thereof), a sulfo group (acid or salt thereof), a phosphono group (acid or salt thereof), a phosphinic acid group or salt thereof, an alkoxycarbonyl group, an aryloxycarbonyl group, respectively. , A carbamoyl group, an acylamino group, a sulfamoyl group, a sulfonylamino group, an alkylthio group, a cyano group, a ureido group, or an ammonium group. )

(2) An image receiving element comprising a neutralizing layer, a neutralization timing layer, an image receiving layer and a release layer, and at least one dye image forming compound on a support having a light-shielding layer are successively combined on a support. A photosensitive element having at least one silver halide emulsion layer, and a color diffusion transfer photographic image forming method for developing and processing an alkaline processing composition between the image receiving element and the photosensitive element. The color diffusion transfer photographic image forming method according to the above (1), comprising at least one kind of the compound represented by the general formula (I).

(3) The alkaline treatment composition according to the above (1), wherein the composition comprises at least one compound selected from aliphatic sulfinic acids or salts thereof and aromatic sulfinic acids or salts thereof. Color diffusion transfer photographic image forming method.

The hydroxylamine derivative represented by the general formula (I) of the present invention is described in many patents as a preservative of a color developing solution for a silver halide color photographic light-sensitive material. However, it is not known or suggested that the hydroxylamine derivative of the present invention has a stain preventing effect on color diffusion transfer photographic light-sensitive materials, especially that it exerts a stain preventing effect when added to an alkaline processing composition. Nor. Also, JP-A-8-262
No. 673 discloses an image forming method using a silver salt diffusion transfer method, wherein a 3-pyrazolidinone compound and a compound represented by the general formula (I) of the present invention are used.
By developing in the presence of a compound represented by the following, a method of obtaining a stable silver image with less fading while promoting the development reaction is described, but the purpose of use is different from the present invention. It is not analogous.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in detail.

Hereinafter, the compound represented by formula (I) of the present invention will be described in detail. The unsubstituted alkyl group represented by R may be linear, branched, or cyclic, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. It is an alkyl group, particularly preferably a linear alkyl group having 1 to 4 carbon atoms. Examples of the unsubstituted alkyl group represented by R include methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-hexyl, cyclohexyl and the like. The unsubstituted alkenyl group represented by R may be linear, branched or cyclic, and preferably has 2 to 10, more preferably 2 to 6, and still more preferably 2 to 4 alkenyl. And particularly preferably a linear alkenyl group having 2 to 4 carbon atoms. Examples of the unsubstituted alkenyl group represented by R include allyl, 2-butenyl, 2-pentenyl and the like. R is preferably a hydrogen atom or -L ²
It is -A ^2, more preferably -L ² -A ^2.

The alkylene group represented by L ¹ and L ² is
They may be the same or different, and may be linear, branched or cyclic. Further, it may have a substituent,
As the substituent, for example, an aryl group (preferably having 6 carbon atoms)
To 12, more preferably 6 to 10 carbon atoms, particularly preferably an aryl group having 6 to 8 carbon atoms, for example, phenyl, p-methylphenyl, etc.), an alkoxy group (preferably 1 to 8 carbon atoms, More preferably, it is an alkoxy group having 1 to 6 carbon atoms, particularly preferably an alkoxy group having 1 to 4 carbon atoms, for example, methoxy, ethoxy, etc.), an aryloxy group (preferably having 6 to 1 carbon atoms).
2, more preferably an aryloxy group having 6 to 10 carbon atoms, particularly preferably 6 to 8 carbon atoms, for example, phenyloxy and the like; an acyl group (preferably having 2 to 12 carbon atoms, more preferably carbon atom). An acyl group having 2 to 10, particularly preferably an acyl group having 2 to 8 carbon atoms, for example, acetyl and the like; an alkoxycarbonyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, particularly preferably Is an alkoxycarbonyl group having 2 to 8 carbon atoms, such as methoxycarbonyl and the like; an acyloxy group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and particularly preferably having 2 to 8 carbon atoms). Acyloxy group such as acetoxy, etc.),

An acylamino group (preferably an acylamino group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, such as acetylamino, etc.), a sulfonylamino group ( It is preferably a sulfonylamino group having 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4 carbon atoms, such as methanesulfonylamino and the like, a sulfamoyl group (preferably 0 carbon atom). From 1
0, more preferably a sulfamoyl group having 0 to 6 carbon atoms, particularly preferably 0 to 4 carbon atoms, such as sulfamoyl and methylsulfamoyl; and a carbamoyl group (preferably having 1 to 10 carbon atoms). Preferably it has 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms.
A carbamoyl group, for example, carbamoyl, methylcarbamoyl and the like), an alkylthio group (preferably an alkylthio group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms). And a sulfonyl group (preferably having 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 4 carbon atoms, such as methanesulfonyl and the like). And a sulfinyl group (preferably having 1 carbon atom).
To 8, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, for example, methanesulfinyl and the like, a hydroxy group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom) , A cyano group, a sulfo group, a carboxyl group, a nitro group, a heterocyclic group (for example, imidazolyl, pyridyl) and the like.

These substituents may be further substituted. When there are two or more substituents, they may be the same or different. The substituent is preferably an alkoxy group, a carboxyl group, a hydroxy group, a halogen atom, a cyano group, or a nitro group, and more preferably an alkoxy group, a carboxyl group, or a hydroxy group. L ¹ and L
^The alkylene group represented by ² is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and still more preferably an alkylene group having 1 to 2 carbon atoms. Examples of the alkylene group include methylene, ethylene, propylene, methylmethylene and the like, more preferably methylene and ethylene, and particularly preferably ethylene. R and L ¹ may be linked to form a ring.

The alkoxycarbonyl group represented by A ¹ and A ² is preferably an alkoxycarbonyl group having 2 to 12, more preferably 2 to 10, and particularly preferably 2 to 8 carbon atoms. Examples include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl and the like. The aryloxycarbonyl group represented by A ¹ and A ² preferably has 7 to 14 carbon atoms, more preferably 7 to 1 carbon atoms.
1, particularly preferably an aryloxycarbonyl group having 2 to 8 carbon atoms, for example, phenoxycarbonyl, 4-
Methylphenoxycarbonyl and the like. The carbamoyl group represented by A ¹ and A ² preferably has 1 carbon atom.
To 10, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as carbamoyl and methylcarbamoyl. A ¹
And the acylamino group represented by A ² is preferably an acylamino group having 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4 carbon atoms, such as acetylamino.

A¹And A^TwoA sulfamoyl group represented by
Preferably has 0 to 10 carbon atoms, more preferably carbon
A sulfa having 0 to 6, particularly preferably 0 to 4 carbon atoms
Moyl group, for example, sulfamoyl, methyl sulf
Amoyl and the like. A ¹And A^TwoRepresented by
The honylamino group preferably has 1 to 10 carbon atoms, more
Preferably 1 to 6 carbon atoms, particularly preferably 1 carbon atom
4 is a sulfonylamino group, for example, methanesulfo
Nylamino and the like. A¹And A^TwoA represented by
The alkylthio group preferably has 1 to 8 carbon atoms, more preferably
Or 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms.
Alkylthio group, for example, methylthio, ethylthio
And the like. A¹And A^TwoUreido group represented by
Preferably has 1 to 10 carbon atoms, more preferably carbon
Ureides having 1 to 6, particularly preferably 1 to 4 carbon atoms
Group, for example, ureido, methylureide and the like.
It is. A¹And A^TwoThe ammonium group represented by
Or from 3 to 12 carbon atoms, more preferably from 3 carbon atoms
9, particularly preferably an ammonio group having 3 to 6 carbon atoms.
For example, trimethylammonio and the like can be mentioned. A¹
And A^TwoPreferably as a carboxyl group, a sulfo group,
Phosphono group, phosphinic acid group, alkoxycarbonyl
Group, an aryloxycarbonyl group, more preferably
Is carboxyl group, sulfo group, phosphono group, alkoxy
Carbonyl group, more preferably carboxyl group, alkoxy
A cyclocarbonyl group, particularly preferably a carboxyl group
It is.

When the carboxyl group, sulfo group, phosphono group and phosphinic acid group represented by A ¹ and A ² in the general formula (I) form respective salts, the cations forming these salts are organic cations. However, it may be an inorganic cation. Specific examples thereof include the following general formula (Ia)
And the same as the specific examples of the cation represented by Ra in the above.

Among the compounds represented by the general formula (I), a compound represented by the general formula (Ia) is preferable.

[0021]

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(In the formula (Ia), L ¹ and L ² have the same meanings as those in the formula (I), and the preferred ranges are also the same as those in the formula (I). Ra and Rb Represents a hydrogen atom, an alkyl group or a cation.)

The alkyl group represented by Ra and Rb is preferably an alkyl group having 1 to 11 carbon atoms, more preferably 1 to 9 carbon atoms, particularly preferably 1 to 7 carbon atoms, for example, methyl, ethyl, n-propyl, n-butyl and the like. The cation represented by Ra and Rb is
Represents an organic or inorganic cation, for example, an alkali metal (Li ⁺ , Na ⁺ , K ⁺ , Cs ^+, etc.), an alkaline earth metal (Mg ²⁺ , Ca ^2+, etc.), ammonium (ammonium, trimethylammonium, triethylammonium) , Tetramethylammonium, tetraethylammonium, tetrabutylammonium, 1,2-ethanediammonium, etc.), pyridinium, phosphonium (tetrabutylphosphonium, etc.) and the like. Ra and Rb are preferably a hydrogen atom or a cation.

Specific examples of the compound represented by formula (I) are shown below, but the present invention is not limited thereto.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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The compound represented by the general formula (I) can be synthesized by subjecting commercially available hydroxylamines to an alkylation reaction (nucleophilic substitution reaction, addition reaction, Mannich reaction). That is, West German Patent 1,159,634, Inor
ganica Chimica Acta 93
Particularly specific methods which can be synthesized according to the methods described in Items 01 to 108 (1984) and the like are described in JP-A-8-262573.

The compound represented by the general formula (I) is preferably 1 × 10 ^{-4 to} 5 × 10 ^-1 mol, more preferably 1 × 10 ^-3 to 1 × 10 ^-1 mol per kg of the alkaline treatment composition. preferable.

Next, the aliphatic sulfinic acid or salts thereof and the aromatic sulfinic acid or salts thereof which can be used in the alkaline treatment composition of the present invention will be described. These sulfinic acids used in the present invention are preferably compounds represented by the following general formula (II).

Formula (II) Y- (SO ₂ M) _{n In the} formula (II), M is a hydrogen atom, an alkali metal atom such as sodium or potassium, an alkaline earth metal such as calcium or magnesium, or triethylamine or trimethylamine. Y represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and n represents 1 or 2.

The total number of carbon atoms of the alkyl group or substituted alkyl group represented by Y is preferably from 5 to 30, more preferably from 8 to 24, and may be linear or branched. Examples thereof include a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, a nitro group, an alkoxy group having an alkyl residue having 1 to 5 carbon atoms, a phenyl group, and a halogen atom (such as a chlorine atom).

The aryl group represented by Y is, for example, a phenyl group or a naphthyl group. Examples of the substituent of the substituted aryl group include an alkyl group having 1 to 18 carbon atoms, an alkenyl group (for example, vinyl group), an alkyl group and the like. Examples thereof include an alkoxy group having a residue of 1 to 5 carbon atoms, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, a nitro group, a phenyl group, and a halogen atom (such as a chlorine atom). Further, the substituent may be a polymer chain.

The sulfinic acids used in the present invention are specifically shown below.

[0039]

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[0040]

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The amount of the sulfinic acid used in the present invention is from 0.02 to 100 mol%, preferably from 10 to 40 mol%, based on the developing agent in the processing composition.

Hereinafter, each component used in the present invention will be sequentially described.

I. Photosensitive Element A) Support The support for the photosensitive element used in the present invention may be any smooth transparent support usually used for photographic photosensitive materials, and examples thereof include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. It is preferable to provide an undercoat layer. Preferably, the support usually contains a trace amount of a dye or a pigment such as titanium oxide to prevent light piping. The thickness of the support is 50-
It is 350 μm, preferably 70 to 210 μm, more preferably 80 to 150 μm. On the back side of the support, if necessary, a curl balance layer or JP-A No.
An oxygen barrier layer described in -78833 can be provided.

B) Light-shielding layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the support and the photosensitive layer. As the light-shielding agent, any material having a light-shielding function is used, and carbon black is preferably used. U.S. Pat. No. 4,615,96
Degradable dyes described in No. 6, etc. may be used. As the binder for coating the light-blocking agent, any binder capable of dispersing carbon black may be used, and gelatin is preferred. As a carbon black raw material, for example, Donnel Vo
et "Carbon Black" MarcelDekker, Inc. (1976)
Any method such as a channel method, a thermal method, and a furnace method described in (1) can be used. Although the particle size of carbon black is not particularly limited,
Those having a wavelength of 1800 nm are preferred. The addition amount of the black pigment as a light-shielding agent may be adjusted according to the sensitivity of the photosensitive material to be shielded from light, but is preferably about 5 to 10 in optical density.

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

(1) Dye-Image-Forming Compound The dye-image-forming compound used in the present invention is a non-diffusible compound which releases a diffusible dye (may be a dye precursor) in connection with the silver phenomenon, or is itself. Changes in the diffusivity of photographic processes, see “Theory of Photographic Process” (The T
heory of the Photographic Process, Macmillan) 4
It is stated in the edition. All of these compounds can be represented by the following general formula (III).

Formula (III) (DYE-Y) _n -Z In formula (III), DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, and Y represents a mere bond or Represents a linking group, and Z represents a difference in diffusivity of the compound represented by (DYE-Y) _n -Z corresponding to or opposite to a photosensitive silver salt having an image-like latent image, or Represents a group having the property of releasing DYE and causing a difference in diffusivity between the released DYE and (DYE-Y) _n -Z, wherein n represents 1 or 2, and n represents 2 Time, two DYs
EY may be the same or different. ｝

By the function of Z, the diffusibility in the silver developing section is improved.
Negative compound and positive compound which becomes diffusible in the undeveloped part
It is roughly divided into things. Specific examples of the negative type Z include development
As a result, those that oxidize and cleave to release diffused dyes
No. Specific examples of Z are disclosed in US Pat. No. 3,928,312.
Nos. 3,993,638 and 4,076,529
Nos. 4,152,153, 4,055,428
Nos. 4,053,312, 4,198,235
Nos. 4,179,291 and 4,149,892
No. 3,844,785, No. 3,443,943
Nos. 3,751,406 and 3,443,939
Nos. 3,443,940 and 3,628,952
Nos. 3,980,479 and 4,183,753
No. 4 _d142,891, 4,278,750
Nos. 4,139,379 and 4,218,368
No. 3,421,964, 4,199,355
No. 4,199,354 and 4,135,929
No. 4,336,322 and 4,139,389
JP-A-53-50736 and JP-A-51-104343.
No. 54-130122, No. 53-110827
Nos. 56-12624, 56-16131, and
Nos. 57-4043, 57-650 and 57-207
No. 35, No. 53-69033, No. 54-130927
Nos. 56-164342, 57-119345, etc.
It is described in.

Among the Z of the negative dye releasing redox compound, a particularly preferred group is an N-substituted sulfamoyl group (an N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). it can. Representative groups of Z are exemplified below, but are not limited thereto.

[0050]

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For positive-type compounds, see Angev. Chem. Inst. Ed. Engl., 22, 191.
(1982). Specific examples include compounds (dye developing agents) which are initially diffusible under alkaline conditions, but are oxidized by development to become non-diffusible. Z useful in this type of compound is disclosed in US Pat.
No. 83,606 are typical. Another type is a type in which a diffusible dye is released by, for example, self-cyclization under alkaline conditions, but the dye is substantially not released when oxidized during development. Specific examples of Z having such a function are described in U.S. Pat. No. 3,980,479 and JP-A-53-69033.
No. 54-130927, U.S. Pat. No. 3,421,9
No. 64 and 4,199,355.

Another type does not release the dye itself, but releases the dye when reduced.
Compounds of this type are used in combination with an electron donor,
The diffusible dye can be released imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. For atomic groups having such a function, see, for example, US Pat. Nos. 4,183,753 and 4,142,891.
No. 4,278,750, 4,139,379
No. 4,218,368, JP-A-53-11082.
7, U.S. Pat. Nos. 4,278,750 and 4,356,
Nos. 249 and 4,358,525, JP-A-53-11
0827, 54-130927, 56-164
No. 342, published technical report 87-6199, European Patent Publication 2
20,746A2.

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

[0054]

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When a compound of this type is used, it is preferably used in combination with a diffusion-resistant electron-donating compound (known as an ED compound) or its precursor (precursor). Examples of ED compounds include, for example, US Pat.
Nos. 263,393 and 4,278,750;
No. 6-138736. Specific examples of other types of dye image-forming substances include the following.

[0056]

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The details are described in US Pat. Nos. 3,719,489 and 4,098,783.

On the other hand, specific examples of the dye represented by DYE of the above general formula are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. , 383, 4,195,992, 4,148,641, 4,148,643 and 4,336,322: JP-A-51-114930,
No. 56-71072: Research Disclosure 1763
No. 0 (1978) and No. 16475 (1977).

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

Examples of cyan dyes: US Pat. No. 3,482,9
No. 72, No. 3,929,760, No. 4,013,63
No. 5, 4,268,625, 4,171,220
Nos. 4,242,435 and 4,142,891
Nos. 4,195,994 and 4,147,544
No. 4,148,642; British Patent 1,551,1
No. 38; JP-A-54-99431, JP-A-52-8827.
No. 53-47823, No. 53-143323,
Nos. 54-99431 and 56-71061; European Patents (EP) 53,037 and 53,040;
Research Disclosure 17,630 (1978) and 16,475 (1977). These compounds are disclosed in JP-A-62-215272.
It can be dispersed by the method described on pages 44 to 146. These dispersions are described in JP-A-62-215272.
Compounds described on pages 37 to 144 may be included.

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

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

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

In the present invention, a spectral sensitizing dye is used in combination with the negative emulsion and the internal latent image type direct positive emulsion.
For specific examples, see JP-A-59-180550,
No. 60-140335, Research Disclosure (RD) 17029, U.S. Patent 1,846,300
No. 2,078,233 and 2,089,129
Nos. 2,165,338 and 2,231,658
No. 2,917,516, 3,352,857
No. 3,411,916, 2,295,276
No. 2,481,698, 2,688,545
Nos. 2,921,067 and 3,282,933
Nos. 3,397,060 and 3,660,103
Nos. 3,335,010 and 3,352,680
Nos. 3,384,486 and 3,623,881
Nos. 3,718,470 and 4,025,349.

(3) Composition of photosensitive layer To reproduce a natural color by the subtractive color method, the above-mentioned dye which provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the above-mentioned spectral sensitizing dye is used. A photosensitive layer comprising at least two of the combination 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 applied as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity range of the emulsion combined therewith, a separate layer is preferred. 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. For example, a layer containing a nucleation development accelerator described in JP-A-60-173541, JP-B-60-1
No. 5267 may be provided to increase the color image density by providing a partition layer, or a reflective layer may be provided to increase the sensitivity of the photosensitive element.

The reflection layer is a layer containing a white pigment and a hydrophilic binder. Preferably, the white pigment is titanium oxide and the hydrophilic binder is gelatin. The coating amount of titanium oxide is 0.1 g / m ^{2 to} 8 g / m ² , preferably 0.2 g / m ^2.
a ^{g / m 2 ~4g / m 2} . An example of the reflection layer is disclosed in
No. 0-91354.

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

When a developer is used in combination with a non-diffusible dye image-forming substance, the intermediate layer preferably contains a non-diffusible reducing agent to prevent diffusion of the oxidized developer. Specific examples thereof include non-diffusible hydroquinone, sulfonamidophenol, and sulfonamidonaphthol, and more specifically, JP-A-50-21249 and JP-A-50-21249.
No. 0-23813, JP-A-49-106329, and JP-A-49-106329.
No. 9-129535, U.S. Pat. No. 2,336,327,
2,360,290, 2,403,721, 2,544,640, 2,732,300, 2,782,659, 2,937,086, and 3 637,393, 3,700,453, British Patent 557,750, JP-A-57-24949, and 58-21249. The dispersing methods are described in JP-A-60-238831 and JP-B-60-18978. Japanese Patent Publication 55-7
In the case of using a compound capable of releasing a diffusible dye by silver ions as described in JP-A-576-576, it is preferable to include a compound that captures silver ions in the intermediate layer.

In the present invention, an anti-irradiation layer, a UV absorber layer, a protective layer and the like are provided as required. In the case of a mono-sheet type color diffusion transfer photographic light-sensitive material, D) an image receiving layer,
E) It is common to provide a white reflective layer.

D) Image receiving layer The dye image receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This may be a single layer or a multilayer structure in which mordants having different mordant powers are applied in layers. This is described in JP-A-61-25255.
No. 1. As the mordant, a polymer mordant is preferable. The polymer mordant is a polymer containing secondary and tertiary amino groups, a polymer containing a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation and having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. Things. The coating amount of the mordant is generally 0.5
10 to 10 g / m ^2, preferably 1.0 to 5.0 g / m ^2, particularly preferably ² to 4 g / m ² . As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and the like are used, and gelatin is preferable. In the image receiving layer, an anti-fading agent described in JP-A Nos. 62-30620, 62-30621 and 62-215272 can be incorporated.

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

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

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

II. Image Receiving Element A) Support As the support of the image receiving element in the present invention, a support that can withstand the processing temperature is used. In general,
Paper and synthetic polymers (films). Specifically, polyethylene terephthalate, polycarbonate,
Synthesis of polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (eg, triacetyl cellulose) or those containing pigments such as titanium oxide in their films, and film-processed synthetic paper made of polypropylene, etc., and synthesis of polyethylene, etc. Mixed paper made from resin pulp and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, Japanese Patent Application Laid-Open No. 62-25 / 1987
The supports described on pages 3159 (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports.

B) Release Layer In the present invention, a release layer is provided in order to peel off the image receiving element in the unit at an arbitrary place after the processing. Therefore, this release layer must be easily peelable after the treatment. Materials for this purpose include, for example, JP-A-47-8237 and JP-A-5-8237.
Nos. 9-220727, 59-229555 and 49
-4653, U.S. Pat. Nos. 3,220,835 and 4,359,518, and JP-A-49-4334, 5
Nos. 6-65133, 45-24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 4,401,746 and 4,366,227. Can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. Examples include hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. Other examples include various natural polymers, such as alginic acid, pectin, gum arabic, and the like. Various modified gelatins such as acetylated gelatin and phthalated gelatin can also be used. Still another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethyl methacrylate, polybutyl methacrylate, or a copolymer thereof, or the like. The release layer may be a single layer or, for example, disclosed in JP-A-59-22.
It may be composed of a plurality of layers as described in JP-A Nos. 0727 and 60-60642.

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

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

Specific examples of the acidic polymer include ethylene,
Copolymers of vinyl monomers such as vinyl acetate and vinyl methyl ether with maleic anhydride and their n-butyl esters, copolymers of butyl acrylate and acrylic acid, cellulose, acetate hydrogendiene phthalate and the like. The polymer acid can be used as a mixture with a hydrophilic polymer. Such polymers include:
Examples include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and polymethylvinylether. Among them, polyvinyl alcohol is preferred. Further, a polymer other than the hydrophilic polymer in the polymer acid,
For example, cellulose acetate or the like may be mixed.

The amount of the polymer acid applied is controlled by the amount of alkali developed between the photosensitive element and the image receiving element. The equivalent ratio of polymer acid to alkali per unit area is 0.9 to
2.0 is preferred. If the amount of the polymer acid is too small, the hue of the transfer dye is changed, and stain is generated in the white d portion. If the amount is too large, inconveniences such as a change in hue and a decrease in light resistance are caused. A more preferred equivalent ratio is 1.
0 to 1.3. If the amount of the hydrophilic polymer to be mixed is too large or too small, the quality of the photograph is deteriorated. The weight ratio of the hydrophilic polymer to the polymer acid is from 0.1 to 10, preferably from 0.3 to 3.0.

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

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

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

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

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

D) Image Receiving Layer The dye receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This may be a single layer or a multilayer structure in which mordants having different mordant powers are applied in layers. This is described in JP-A-61-25255.
No. 1 and JP-A-4-73648. As the mordant, a polymer mordant is preferable. The polymer mordant is a polymer having a secondary or tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation, or the like, having a molecular weight of 5,000 to 500,000.
The following, particularly preferably 10,000 to 300,
000 or less. The coating amount of the mordant is generally 0.5 to 10 g / m ² , preferably 1.0 to 5.0 g.
/ M ² , particularly preferably ² to 4 g / m ² .

As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone and the like are used, and gelatin is preferred. The image receiving layer is described in JP-A-62-263020.
No. 62-30621, JP-A-62-215272.
The anti-fading agent described in (1) can be incorporated.

E) Others In addition to the layer having a neutralizing function, a backing layer, an intermediate layer and the like may be provided as a layer having an auxiliary function. The back layer is provided for adjusting curl, providing slipperiness, and providing a light-shielding function. In the case of a mono-sheet type color diffusion transfer photographic material, a cover sheet having a neutralizing function is generally used instead of the image receiving element. The cover sheet includes a support, a layer having a neutralizing function, a timing layer, and other layers.

III. Alkaline Processing Composition The processing composition used in the present invention is developed uniformly between the photosensitive element and the image receiving element after exposure of the photosensitive element, and develops the photosensitive layer. For this reason, in the composition, in addition to the hydroxyamines and sulfinic acids represented by the general formula (I), generally, an alkali, a thickener, a developing agent, and further, Development accelerator, development inhibitor,
Contains an antioxidant to prevent the deterioration of the developer.

The alkali is sufficient to adjust the pH of the solution to 12 to 14, and includes a hydroxide of an alkali metal (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide),
Examples thereof include alkali metal phosphates (eg, potassium phosphate), guanidines, and quaternary amine hydroxides (eg, tetramethylammonium hydroxide). Of these, potassium hydroxide and sodium hydroxide are preferable. The thickener is required to spread the processing solution uniformly and to maintain the close contact between the photosensitive layer and the cover sheet. For example, polyvinyl alcohol, hydroxyethyl cellulose, an alkali metal salt of carboxymethyl cellulose is used,
Preferably, hydroxyethyl cellulose and sodium carboxymethyl cellulose are used.

As the preferred developing agent, any one can be used as long as it cross-oxidizes the dye image-forming compound and does not substantially generate stain even when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in the form of a precursor. These developing agents may be contained in a suitable layer of the photosensitive element, or may be contained in an alkaline processing solution. Specific examples of the compound include aminophenols and pyrazolidinones, and among them, pyrazolidinones are particularly preferable because they generate less stain. For example, 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3'-methyl-phenyl) -4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidinone,
And the like. In addition, these alkaline liquid compositions have a developed thickness (amount of the processing liquid per m ² after transferring the processing liquid) of 20 μm.
It is desirable that the image is transferred onto a photosensitive material at a thickness of about 200 μm.
The processing temperature when processing the light-sensitive material of the present invention is 0 to 50.
C is preferable, and 0 to 40 C is more preferable.

JP-A No. 62-215272, 72, for any of the photosensitive element, the image receiving element and the alkaline processing composition.
To 91, a hardener described on pages 146 to 155, a surfactant described on pages 201 to 210, 210-2.
A fluorine-containing compound described on page 22; a thickener described on pages 225 to 227; an antistatic agent described on pages 227 to 230;
Polymer latex described on page 239, matting agent described on page 240 and the like can be included.

[0092]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these.

Example 1 A photosensitive element (101) was prepared by coating on a 100 μm transparent polyethylene terephthalate film support in the following layer configuration.

[0094] Back layer side: (a) the light-shielding layer containing carbon black 6.0 g / m ² and gelatin 2.0 g / m ^2. (B) A protective layer containing 0.5 g / m ² of gelatin.

[0095] Emulsion layer side: (1) titanium dioxide 3.7 g / m ^2, the layer containing a development inhibitor releasing compound 0.15 g / m ² and gelatin 0.5 g / m ² below.

[0096]

Embedded image

(2) The following cyan dye releasing redox compound 0.47 g / m ² , tricyclohexyl phosphate 0.07 g / m ² , the following dispersing aid (A) 0.05 g / m ²
a coloring material layer containing m ² , the following dispersing aid (B) 0.06 g / m ² , and gelatin 0.5 g / m ² .

[0098]

Embedded image

(3) Layer containing 0.5 g / m ² of gelatin. (4) Red-sensitive internal latent type direct positive silver bromide emulsion (average grain size: 0.65 μm, silver amount: 0.12 g / m ² ), gelatin: 0.3 g / m ² , and the following nucleating agent: 0.004 mg / m ² and 2-sulfo -5-n-pentadecylhydroquinone sodium salt 0.04 g / m ² red-sensitive emulsion layer containing a.

[0100]

Embedded image

(5) Red-sensitive internal latent type direct positive silver bromide emulsion (average grain size 0.98 μm, silver amount 0.28 g /
m ^2), gelatin 0.5 g / m ^2, and the layer (4) and the red-sensitive emulsion layer containing the same nucleating agent 0.005 mg / m ^2. (6) 2,5-di-t-pentadecylhydroquinone 0.82 g / m ² , trihexyl phosphate 0.1 g /
color mixing prevention layer containing m ^2, and gelatin 0.3 g / m ^2. (7) An intermediate layer containing 0.2 g / m ² of gelatin. (8) The following magenta dye-releasing redox compound is used in 0.1.
54 g / m ² , 0.05 g of the same dispersing aid (A) as in layer (2)
/ M ² , a colorant layer containing 0.05 g / m ^{2 of} a dispersing aid (B) and 0.7 g / m ² of gelatin.

[0102]

Embedded image

(9) Green-sensitive internal latent type direct positive silver bromide emulsion (average grain size: 0.65 μm, silver amount: 0.15 g /
m ^2), gelatin 0.3 g / m ^2, the layer (4) and the same nucleating agent 0.015 mg / m ² and 2-sulfo -5-n-pentadecylhydroquinone sodium salt 0.04 g / m ² Green sensitive emulsion layer. (10) Green-sensitive internal latent type direct positive silver bromide emulsion (average grain size 0.98 μm, silver amount 0.29 g / m ² ), gelatin 0.6 g / m ² , same nucleation as layer (4) Agent 0.007mg / m ²
And a green-sensitive emulsion layer containing 0.03 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt. (11) The same layer as (6). (12) The same layer as (7). (13) 0.52 g / m ² of a yellow dye-releasing redox compound having the following structure, tricyclohexyl phosphate 0.1.
13 g / m ² , 0.05 g of the same dispersing aid (A) as in layer (2)
/ M ^2, a dispersion aid (B) color material layer containing 0.03 g / m ² and gelatin 0.5 g / m ^2.

[0104]

Embedded image

(14) Blue-sensitive internal latent type direct positive silver bromide emulsion (average grain size: 0.65 μm, silver amount: 0.27 g /
m ^2), gelatin 0.5 g / m ^2, the layer (4) and the same nucleating agent 0.014 mg / m ² and 2-sulfo -5-n-pentadecylhydroquinone sodium salt 0.03 g / m ² Blue-sensitive emulsion layer. (15) Blue-sensitive internal latent type direct positive silver bromide emulsion (average grain size 0.98 μm, silver amount 0.34 g / m ² ), gelatin 0.5 g / m ² , same nucleation as layer (4) Agent 0.009mg / m ²
And a blue-sensitive emulsion layer containing 0.03 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt. (16) Polymethylmethacrylate spherical latex (average particle size 4 μm) 0.2 g / m ² and gelatin 0.4 g / m ²
A protective layer containing.

Next, an image receiving element (201) was prepared by coating on a 150 μm paper support having 30 μm polyethylene laminated on both sides in the following layer configuration.

[0107] Back layer side: (a) the light-shielding layer containing carbon black 4.0 g / m ² and gelatin 2.0 g / m ^2. (B) Titanium dioxide 8.0 g / m ² and gelatin 1.0
White layer containing g / m ² . (C) A protective layer containing 0.6 g / m ² of gelatin.

Image receiving layer side: (1) A neutralizing layer containing 22 g / m ² of an acrylic acid / butyl acrylate copolymer (molar ratio: 8: 2, average molecular weight: 50,000). (2) diacetyl cellulose (degree of acetylation: 51.3%) 4.
27 g / m ² and 0.23 g of a styrene / maleic anhydride copolymer (molar ratio 1: 1, average molecular weight 10,000)
/ M ² containing timing layer. (3) Poly 2-hydroxyethyl methacrylate 0.4
An intermediate layer containing g / m ² . (4) Polymer latex (styrene / butyl acrylate / N-methylol acrylamide in a weight ratio of 49.7)
/42.3/8 emulsion polymerization) 0.96 g /
m ² and polymer latex (methyl methacrylate /
Acrylic acid / N-methylolacrylamide in a weight ratio of 9
(3/3/4 emulsion polymerization) Timing layer containing 0.64 g / m ² . (5) The following mordant (A) 2.8 g / m ² , the following hardener (B) 0.03 g / m ² , and the following coating aid (C) 0.1 g / m
mordant layer containing m ² and 2.8 g / m ² of gelatin.

[0109]

Embedded image

(6) Acrylic acid / butyl methacrylate copolymer (molar ratio: 85:15, average molecular weight: 100,00
Release layer containing 0).

Further, a comparative alkaline treatment composition (30 g) was prepared by filling 1 g of a treatment solution having the following composition in a pod of aluminum foil laminated with vinyl chloride under a nitrogen atmosphere.
1) was produced.

Hydroxyethyl cellulose 42 g Zinc nitrate · 6H ₂ O 0.4 g 5-methylbenzotriazole 5.4 g Benzyl alcohol 3.4 cc Titanium dioxide 1.2 g Aluminum nitrate · 9H ₂ O 15 g Potassium sulfite 2.0 g 1-phenyl -4-hydroxy-4-hydroxymethyl-3-pyrazolidone 13.0 g potassium hydroxide 63 g water 854 cc

Compounds (I-2), (I-5) and (I-5) represented by the general formula (I) of the present invention are added to the above-mentioned comparative alkaline composition.
(I-14), (I-19), (I-24), (I-29),
(I-43), (I-48), (I-68) and (I-70)
Is 5 × 10 per kg of the alkaline treatment composition.
^-Alkaline treatment composition (302) added by ³ moles
(311) was produced.

Next, after imagewise exposure is given to the photosensitive element (101), the image receiving element (201) is superposed, and the thickness of the alkaline processing composition (301) to (311) is increased to 60 μm between the two elements. It was processed as follows. Processing at 25 ° C
90 seconds after processing, the photosensitive element and the image receiving element are peeled off,
Two minutes later, the minimum yellow density and minimum magenta density were measured. Table 1 shows the results.

[0115]

[Table 1]

As is clear from Table 1, when treated with the alkaline treatment composition containing the compound represented by the general formula (I) of the present invention, the yellow minimum density and the magenta minimum density immediately after the treatment are low. An image was obtained.

Example 2 The compounds (I-5) and (I) represented by the general formula (I) of the present invention were added to the comparative alkaline treatment composition (310) of Example 1.
-19) in 2 parts per kg of the alkaline treatment composition
× 10 ^-3 mol, and added to the alkaline treatment composition (31
2) and (313) were created. Next, the sulfinic acids (II-1) of the present invention are added to the alkaline treatment composition (312),
Each of (II-2), (II-9) and (II-16) was added in an amount of 1 × 10 ^-2 mol / kg of the alkaline treatment composition ((II
-16) was added by 2.06 g) to prepare alkaline treatment compositions (314), (315), (316) and (317). Similarly, the sulfinic acids (II-1), (II-2) and (II-) of the present invention are added to the alkaline treatment composition (313).
9) and (II-16) were added in an amount of 1 × 10 ^-2 mol per kg of the alkaline treatment composition (2.06 g of (II-16)) to add the alkaline treatment compositions (318), (319),
(320) and (321) were created. In the same manner as in Example 1, the photosensitive element (101) and the image receiving element (201) were combined and exposed and developed. The film was peeled 90 seconds after the development at 25 ° C., and two minutes later, the minimum yellow density and the minimum magenta density were measured. Table 2 shows the obtained results.

[0118]

[Table 2]

As is clear from Table 2, when the alkaline treatment composition containing the compound represented by the general formula (I) of the present invention and the sulfinic acid of the present invention was used, the minimum yellow density immediately after the treatment was used. And a good image having a low magenta minimum density was obtained, but particularly preferable results were obtained when the minimum density of the magenta image was low.

Example 3 First, a method for preparing a silver halide emulsion will be described. The following eight kinds of silver halide emulsion grains (emulsion-A to emulsion-F) and emulsion-T,
U was prepared.

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

Next, core chemical sensitization was performed in the following container and formulation. 1. Tank: hemispherical bottom with metal surface made of Teflon coated with a thickness of 120 μm by fluoro resin FEP developed by Du Pont. 2. Stirring impeller: Seamless, integral type, propeller type with Teflon coated metal surface.

3. Prescription 1 mg of sodium thiosulfate and 3 ml of an aqueous solution obtained by dissolving 90 mg of potassium tetrachloroaurate and 1.2 g of potassium bromide in 1000 ml of water were added to the above-mentioned preparation solution of octahedral silver bromide crystals.
Chemical sensitization treatment was performed by heating at 75 ° C. for 80 minutes. The emulsion solution thus chemically sensitized was treated with 0.1%.
After adding 15 M of potassium bromide, a 0.9 M aqueous solution of silver nitrate and a 0.9 M aqueous solution of potassium bromide are added in a controlled double jet method while maintaining the temperature at 75 ° C. as in the preparation of the core particles. While adjusting the rate of addition of the aqueous potassium bromide solution to 30 to 370 ml, an aqueous solution of silver nitrate (670 ml) was added over 70 minutes. The emulsion was washed with water by a conventional flocculation method, and the above-mentioned gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added thereto, and the average particle size (equivalent sphere size) was about 1.2 μm.
(Hereinafter referred to as internal latent image type core / shell particles).

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

Preparation of emulsions BF (octahedral internal latent image type direct positive emulsion): In the preparation method of emulsion-A, the addition time of an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were changed, and the amounts of added chemicals were changed. Was carried out to obtain an octahedral internal latent image type direct positive silver halide emulsion having a uniform particle size having an average particle diameter (equivalent sphere diameter) shown in Table 3.

[0126]

[Table 3]

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

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

Next, core chemical sensitization was performed in the following container and formulation. 1. Tank: Fluororesin material F developed by DuPont for metal surface
Hemisphere bottom shape with Teflon coating with thickness 120μm by EP. 2. Stirring impeller: Seamless, integral type, propeller type with Teflon coated metal surface.

[0130] 3. Formulation To 200 g of the above hexagonal plate-shaped core emulsion, 1300 ml of water, 0.11 M of potassium bromide and 40 g of deionized gelatin were added, and the temperature was raised to 75 ° C., followed by 0.3 g of 3,6-dithia-1,8-octanediol. Then, 2.4 mg of an aqueous solution of 10 mg of sodium benzenethiosulfate, 90 mg of potassium tetrachloroaurate and 1.2 g of potassium bromide in 1000 ml of water, and 15 mg of lead acetate (added as an aqueous solution) were added.
A chemical sensitization treatment was performed by heating for 80 minutes. A 2M silver nitrate aqueous solution and a 2.5M aqueous potassium bromide solution were added to the chemically sensitized core particles in the same manner as in the preparation of the core particles, and an aqueous potassium bromide solution was added so that the pBr was 2.2. While adjusting the speed, the mixture was added by the double jet method at an accelerated flow rate (the flow rate at the end was three times the flow rate at the start) (the amount of the aqueous silver nitrate solution used was 810 ml).

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

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

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

Using emulsions AF, T and U, the following Table 4
A photosensitive element (sample 101) having the structure shown in Table 7 was prepared. The sensitizing dye was used at the end of the shell chemical sensitization as shown in Table 8 below.
And the dispersion form, addition temperature, and amount shown in Table 1.

[0135]

[Table 4]

[0136]

[Table 5]

[0137]

[Table 6]

[0138]

[Table 7]

[0139]

[Table 8]

[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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The alkaline treatment composition (501) was prepared by the following method. 0.8 g of a treatment liquid having the following composition was filled in a container which can be broken by pressure. 695 g of water 1-p-tolyl-4-hydroxymethyl-4-methyl 7.00 g -3-pyrazolidin-1-one 1-phenyl-4-hydroxymethyl-4-methyl 9.85 g -3-pyrazolidin-1-one 5-methylbenzotriazole 2.50 g zinc nitrate hexahydrate 0.60 g potassium sulfite 1.90 g aluminum nitrate nonahydrate 0.60 g carboxymethylcellulose Na salt 56.0 g potassium hydroxide 55.0 g carbon black 160 g anionic surfactant 8.60 g Anionic surfactant 0.03 g Alkyl-modified PVA (manufactured by Kuraray Co., Ltd.) 0.06 g Cationic polymer 1.05 g

[0154]

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The neutralization timing time of the cover sheet was measured as follows.

[0156] creating the pH indicator coating film thymolphthalein the pH indicator coating film Polyethylene terephthalate transparent support on applying an indicator layer containing 0.2 g / m ² and gelatin 7.0 g / m ^2.

Alkaline Processing Solution for Neutralization Timing Time Measurement The formulation of the alkaline processing solution is shown below.

0.8 g of a treating solution having the following composition was filled in a container which can be broken under pressure. Carboxymethylcellulose Na salt 58 g Potassium hydroxide (28% aqueous solution) 200 cc Water 830 cc

Each of the transparent cover sheets was opposed to the above-mentioned film coated with the pH indicator, and the alkaline processing solution for measuring the neutralization timing time was 75 μm thick in the meantime.
m. A predetermined time “neutralization timing time” required for the reflection density of the high pH color (blue) of thymolphthalein to decrease by half after the neutralization was measured at 25 ° C.

Preparation of a cover sheet A cover sheet (601) was prepared by coating a transparent support having a thickness of 75 μm with a layer constitution as shown in Table 9.

[0161]

[Table 9]

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

[0163]

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[0164]

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Compounds (I-5) and (I-19) represented by the general formula (I) of the present invention were added to the alkaline treatment composition (501) in an amount of 2 × 10 ^-3 mol / kg of the alkaline treatment composition. The alkaline treatment composition (5
02) and (503). Next, the sulfinic acids (II-2) of the present invention are added to the alkaline treatment composition (502).
And (II-16) in an amount of 1 × 10 ^-2 mol / kg of alkaline treatment composition (2.06 g of (II-16))
Alkaline treatment compositions (504) and (50)
5) was created. Similarly, the alkaline treatment composition (50
3) The sulfinic acids (II-2) and (II-1) of the present invention
6) is 1 × per 1 kg of the alkaline treatment composition.
10 ^-2 mol (2.06 g of (II-16)) was added to prepare alkaline treatment compositions (506) and (507). Next, after the photosensitive element (401) is subjected to imagewise exposure, the cover sheet (601) is overlaid, and the alkaline processing compositions (501) to (507) are each placed between the two elements so as to have a thickness of 55 μm. Expanded. The processing was performed at 25 ° C., and the minimum density of the yellow image was measured 2 hours after development from the photosensitive element side of the superposed unit. Table 10 shows the obtained results.

[0166]

[Table 10]

As is clear from Table 10, when the compound represented by the general formula (I) of the present invention is added, a favorable result with a low yellow stain is obtained, and when a sulfinic acid is further added, the result is even higher. Good results with low yellow stain were obtained.

[0168]

According to the present invention, when a color diffusion transfer photographic light-sensitive material is processed, a preferable image having a low stain after peeling can be obtained.

Claims (3)

[Claims] 1. A color diffusion transfer photographic image forming method for processing a photosensitive element using an alkaline processing composition, comprising at least one compound represented by the following general formula (I). Embedded image (In the formula (I), R represents a hydrogen atom, an unsubstituted alkyl group, an unsubstituted alkenyl group, or -L ² -A ^2. L ¹ and L ² each represent an alkylene group. A ¹ and A
² is a carboxyl group (acid or salt thereof),
Sulfo group (acid or its salt), phosphono group (acid or its salt), phosphinic acid group or its salt, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylamino group, sulfamoyl group, sulfonylamino group, alkylthio group , A cyano group, a ureido group, or an ammonium group. ) 2. An image receiving element comprising a neutralizing layer, a neutralizing timing layer, an image receiving layer, and a release layer, and at least one dye image forming compound on a support having a light-shielding layer. A light-sensitive element having at least one silver halide emulsion layer, and a color diffusion transfer photographic image forming method for developing and processing an alkaline processing composition between the image receiving element and the photosensitive element, wherein the alkaline processing composition is The color diffusion transfer photographic image forming method according to claim 1, comprising at least one compound represented by the general formula (I). 3. The color according to claim 1, wherein the alkaline treatment composition contains at least one compound selected from aliphatic sulfinic acids or salts thereof and aromatic sulfinic acids or salts thereof. Diffusion transfer photographic image forming method.