JPH06332131A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To provide a redox compound capable of releasing a dye and forming a diffusion transfer image high in transfer density and superior in sharpness. CONSTITUTION:The silver halide photosensitive material contains the compound represented by the formula in which R<1> is alkyl; R<2> is alkyl, cycloalkyl, aralkyl, or aryl; X is H or R<3>SO2-; and R<3> is 1-3 C alkyl.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an o-sulfonamidophenol derivative or a pyrazolone azo dye derivative useful for a diffusion transfer type silver halide light-sensitive material. More specifically, it relates to an o-sulfonamidophenol derivative which releases a diffusible dye by a redox reaction following development of silver halide, and a light-sensitive material containing the same or a pyrazolone azo dye derivative, and an image forming method using the same.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication No. 52-7727 describes an image forming method using a redox compound which releases a pyrazolone azo dye. The dye-releasing redox compound specifically mentioned here is a p-compound in which a dye moiety and a non-diffusible naphthol moiety are bonded via a p-sulfonamide group.
It is sulfonamide naphthol. However, these dye-releasing redox compounds have a problem that the transfer density is not sufficient in terms of photographic performance and yellow stain is generated.
An image forming method in which a dye is released from an o-sulfonamidophenol type redox mother nucleus for the purpose of solving these problems is disclosed in JP-A-56-71072. According to a follow-up test conducted by the present inventors, the compound disclosed herein is disclosed in JP-A-52-77
The problem in photographic performance seen in the compound described in No. 27 can be solved to a large extent. However, in consideration of shortening the processing time, it was necessary to further increase the transfer speed. The invention improved in this respect is disclosed in JP-A-61-25255.
No. 0 disclosed. In the dye-releasing redox compound shown here, although the transfer speed is certainly high, the sharpness is deteriorated, and it is clear from the inventor's additional test that the compatibility of the dye transfer speed and the sharpness is insufficient. Became.

[0003]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a light-sensitive material which forms an image having a high dye transfer speed and an excellent sharpness. A second object of the present invention is to provide a light-sensitive material having high transfer density and less stain. A third object of the present invention is to provide a light-sensitive material in which the fastness of the dye is high and the hue change is small. A fourth object of the present invention is to provide a light-sensitive material having a short processing time. Another object of the present invention is to provide a dye or a dye-releasing redox compound having high fastness and small hue change.

[0004]

The objects of the present invention are as follows (1)
Achieved by (5). (1) A silver halide light-sensitive material containing a compound represented by the following general formula (I).

[0005]

[Chemical 4]

(In the formula, R ¹ represents an alkyl group, R ² represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. X represents a hydrogen atom or R ³ SO ₂
Represents a group. R ³ represents an alkyl group having 1 to 3 carbon atoms. ) (2) A dye-releasing redox compound represented by the general formula (I) according to (1). (3) A silver halide light-sensitive material characterized by using a dye represented by the following general formula (II) for image formation.

[0007]

[Chemical 5]

(Wherein X has the same meaning as in general formula (I).) (4) A dye represented by general formula (II) described in (3). (5) The compound represented by the general formula (I) and the following general formula
A silver halide light-sensitive material containing at least one compound represented by formula (III).

[0009]

[Chemical 6]

(In the formula, Y is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group,
Acylamino group, sulfonylamino group, ureido group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, urethane group, amino group, sulfamoylamino group, cyano group, hydroxyl group, It represents a phosphonate group and a heterocyclic group, and n represents an integer of 1 to 5. When n is 2, 3, 4 or 5, Y may be the same or different. When n is 2, 3, 4 or 5, two Y's may combine with each other to form a saturated or unsaturated ring.
Further, the above substituents may be substituted with other substituents. )

The compound represented by formula (I) will be described in detail.

The group represented by R ¹ in the general formula (I) represents an alkyl group (methyl, i-propyl, t-butyl, dodecyl, hexadecyl, eicosyl, 2-hexyldecyl, etc.). The group represented by R ¹ preferably has a total carbon number of 6 or more and 40 or less with the group represented by R ² described later, more preferably 10 or more and 35 or less, and particularly preferably 16 or more 30. It is the following.

The group represented by R ² is an alkyl group (methyl, i-propyl, t-butyl, dodecyl, t-octyl, hexadecyl, eicosyl, 2-hexyldecyl, etc.), a cycloalkyl group (cyclohexyl, 1-methylcyclo). Propyl, 1-adamantyl and the like), aralkyl group (benzyl, 2-phenethyl and the like), or aryl group (phenyl, 2-naphthyl and the like). Of these, R ² is preferably an alkyl group or a cycloalkyl group, more preferably a secondary alkyl group, a tertiary alkyl group or a monocyclic cycloalkyl group. Particularly preferred is a tertiary alkyl group (among others, t-butyl) or a cyclohexyl group. Most preferably, it is a cyclohexyl group.

The group represented by R ¹ O- and the group represented by R ² are preferably located at the m-position of the hydroxyl group (p-position of the sulfonamide group) and the p-position of the hydroxyl group (m-position of the sulfonamide group), respectively. Particularly preferably, the group represented by R ¹ O- is the m-position of the hydroxyl group (p-position of the sulfonamide group) and the group represented by R ² is the p-position of the hydroxyl group (m- of the sulfonamide group).
Rank).

The group represented by X is a hydrogen atom or R ³
It represents a group - SO _2. Here, R ₃ represents an alkyl group having 1 to 3 carbon atoms (methyl, ethyl, propyl, i-propyl). X is preferably a hydrogen atom or a methanesulfonyl group, and particularly preferably a hydrogen atom.

The compound represented by the general formula (II) will be described. The compound represented by the general formula (II) is a diffusible dye released from the oxidant of the compound represented by the general formula (I) during photographic processing, whereby a transferred image is formed. The substituent X in the general formula (II) is represented by the general formula (I).
Is synonymous with.

The compound represented by formula (III) is described in detail below. Y is a hydrogen atom, a halogen atom (chlorine, bromine, etc.), an alkyl group (an alkyl group having 1 to 30 carbon atoms, methyl, t-octyl, dodecyl, 2-hexyldecyl, methoxydecyl, etc.), a cycloalkyl group (cyclopentyl, etc.). , Cyclohexyl, etc.), aralkyl group (benzyl, 2-phenethyl, etc.), alkenyl group (vinyl, allyl, crotyl, etc.), aryl group (phenyl, naphthyl, 4-octyloxyphenyl, 3-hexadecylphenyl, etc.), alkoxy group (C1-C30, methoxy, 2-ethylhexyloxy, 2-dodecyloxyethoxy, etc.)

Aryloxy group (phenoxy, 4-t-
Octylphenoxy, etc.), acylamino groups (acetamide, N-ethyl-dodecane amide, 2-n-heptyl undecane amide, 4-t-butylbenzamide, 2-
(2,4-di-t-amylphenoxy) butanamide, etc.), sulfonylamide group (ethanesulfonamide, 2
-Octyloxy-5-t-octylbenzenesulfonamide, hexadecylsulfonamide, etc.), ureido group (3-hexadecylureido, 3,3-dioctylureido etc.), alkylthio group (ethylthio, dodecylthio etc.)

Arylthio groups (feterthio, 4-ethoxyphenylthio, etc.), alkoxycarbonyl groups (ethoxycarbonyl, hexadecyloxycarbonyl, 2-
Hexyldecyloxycarbonyl, etc.), carbamoyl group (dimethylcarbamoyl, 3-phenoxypropylcarbamoyl, dioctylcarbamoyl, etc.), sulfamoyl group (dimethylsulfamoyl, morpholinosulfonyl, dioctylsulfamoyl, hexadecylsulfamoyl, etc.), acyl group (Propionyl, benzoyl, etc.), sulfonyl group (methanesulfonyl, dodecylsulfonyl, etc.), urethane group (hexadecylurethane, 2-
Hexyldecyl urethane, etc.), amino group (dioctylamino, N-ethyl-N-dodecylamino, 4-methoxyanilino, etc.), sulfamoylamino group (3,3-dioctylaminosulfamoyl, butylaminosulfamoyl) Etc.), heterocyclic (α-pyridyl, 2-furfuryl, etc.), hydroxyl group, phosphonic acid ester group (dicyclohexylphosphonic acid ester, di-n-octylphosphonic acid ester, etc.).

A preferred example of the compound represented by the general formula (III) is a diffusion resistant compound. The diffusion-resistant compound is a compound having a group in the molecule that makes the molecular weight sufficiently large in order to immobilize the molecule in the added layer. Usually, the total carbon number is 8 to 30, preferably 10 to 22.
Or an aryl group having a substituent having a total carbon number of 4 to 20 is used, and a plurality of these diffusion resistant groups may be contained.

The compounds represented by the general formulas (I) and (II) are Y
The group represented by may form a dimer or a multimer which is bonded to each other via a divalent or higher valent group.

Preferred among these Y's are an alkyl group having 10 to 22 carbon atoms, an alkoxy group having 10 to 22 carbon atoms, an alkoxycarbonyl group having 10 to 30 carbon atoms, an acylamino group having 10 to 30 carbon atoms, Examples thereof include urethane groups having 10 to 30 carbon atoms. At least one of the ortho positions (including the peri position in the case of naphthalene) of the sulfamoyl group is preferably a hydrogen atom, and more preferably both ortho positions are hydrogen atoms.

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

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

Exemplary compounds of general formula (III)

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

[0042]

[Chemical 20]

The compound represented by formula (I) of the present invention is preferably used in an amount of 0.1 to 10 mmol, and particularly preferably 0.1 to ² mmol, per 1 m ² of the light-sensitive material. The compound represented by the general formula (III) of the present invention is 0.1 to 500 mol%, preferably 20 mol% to 300 mol%, more preferably 50 mol% per mol of the compound represented by the general formula (I).
˜200 mol%.

The compound represented by the general formula (I) of the present invention can be synthesized according to the method described in JP-A-56-16131 and JP-A-56-71072. More specifically, it can be synthesized by the reaction of aniline derived from o-aminophenol or o-sulfonamidophenol with sulfonyl chloride derived from an azo dye of pyrazolone. It can also be synthesized by reacting a diazonium salt of aniline derived from o-sulfonamidophenol with pyrazolone.

The compound represented by the general formula (II) can be synthesized by reacting a sulfonyl chloride derived from an azo dye of pyrazolone with aniline or ammonia. The compound represented by the general formula (III) can be synthesized, for example, according to the method described in Japanese Examined Patent Publication No. 4-13701.

Typical synthetic examples of the compounds represented by the general formulas (I) to (III) are shown below. (Synthesis Example 1) Synthesis of Exemplified Compound (S-1)

[0047]

[Chemical 21]

S-1a (46.8 g) and m-nitrobenzenesulfonyl chloride (24.4 g) were suspended in N, N-dimethylacetamide (200 ml) under a nitrogen atmosphere. After cooling these mixtures with ice, pyridine (2
4.2 ml) was added dropwise. After a further 30 minutes, ethyl acetate (200 ml) and water (200 ml) were added to the system to separate the aqueous layer. The organic layer is water (250 ml x 1) and saturated saline solution (20
A solution of the crude S-1b product in ethyl acetate was obtained by washing with 0 ml × 1).

Next, reduced iron (50 g) and ammonium chloride (1.2 g), water (40 ml) and i-propanol (31
A solution of S-1b in ethyl acetate was added dropwise to a reflux mixture consisting of 0 ml). After refluxing for a further 2 hours, the reaction solution
After cooling to 0 ° C., the reaction solution was filtered through Celite and washed with methanol (300 ml). After cooling to room temperature, water (2
(00 ml) was added to precipitate crystals. The crystals were collected by filtration and dried to obtain 49 g of S-1c.

Next, under a nitrogen atmosphere, S-1c (12.9 g)
The mixture consisting of S-1d (7.75 g) and N, N-dimethylacetamide (66 ml) was cooled with ice, and α-picoline (5.9 ml) was added. 2N after reacting at room temperature for 4 hours
30 ml of hydrochloric acid, ethyl acetate (200 ml), water (200 ml)
Was added. After separating the water layer, the organic layer is further added with water (200 ml).
It was washed twice with. The organic layer was concentrated and then purified by silica gel column chromatography using ethyl acetate-dichloromethane (1:10, volume ratio) as an eluent to obtain 15.4 g of Exemplified compound S-1. mp193-195
° C. Exemplified compound S-4 was synthesized in the same manner. mp1
05 ° C. (Synthesis Example 2) Synthesis of Exemplified Compound S-3

[0051]

[Chemical formula 22]

Synthesis was carried out in the same manner as in Synthesis Example 1 by the route of Scheme 2. mp198-200 ° C. (Synthesis Example 3) Synthesis of Exemplified Compound S-5

[0053]

[Chemical formula 23]

S-1a (187.0 g) and p-acetylaminobenzenesulfonyl chloride (93.5 g) were mixed with N, N-dimethylacetamide (600 m) under a nitrogen atmosphere.
l) mixed in. This mixture was ice-cooled, 2,6-lutidine (93.2 ml) was added dropwise, and the mixture was reacted for 1 hour and further at room temperature for 2 hours. The reaction solution was poured into ice water (2 liters) and the precipitated crystals were collected by filtration to give S-5a (245
g) crude crystals were obtained.

Next, S-5a (126 g) was added to concentrated hydrochloric acid (85
The reaction was carried out for 6 hours under reflux in ethanol (1 liter) containing (ml). Then, about 0.6 liter of ethanol was distilled off under normal pressure. Water (0.4 liters) after cooling the residue to room temperature
Was added, and the crystals were collected by filtration and washed with a small amount of methanol to obtain crude crystals of S-5b (115 g).

S-5b (12.5 g) and S-5c (7.
76 g) were mixed in N, N-dimethylacetamide (60 ml) under nitrogen atmosphere and the mixture was cooled with ice water. 2,6-lutidine (5.82 ml) was added thereto, and the mixture was stirred for 2 hours, then at room temperature for 10 hours, and left overnight. 2N Hydrochloric acid (50 ml), ethyl acetate (150 ml) and water (300 ml) were added to the reaction mixture, and the aqueous layer was separated. After that, Synthesis Example 1
Exemplified compound S-5 (1
1.2 g) was obtained. mp 182-184 ° C. (Synthesis Example 4) Synthesis of Exemplified Compound D-1

[0057]

[Chemical formula 24]

D-1a (4.0 g) and S-1d (9.0)
g) was dissolved in N, N-dimethylacetamide (40 ml), and after cooling with ice, 2,6-lutidine (4.0 ml) was added. After reacting for 3 hours at room temperature, 2N hydrochloric acid (10 ml), ethyl acetate (100 ml) and water (100 ml) were added. After separating the aqueous layer, the organic layer was washed twice more with water (150 ml) and concentrated. Exemplified compound D by recrystallization from methanol
8.2 g of -1 was obtained. mp 246-248 ° C. D-2 was synthesized by the same method. mp 208 ° C.

(Synthesis Example 5) Synthesis of Exemplified Compound K-12 2- (2,4-di-t- while stirring to a solution of 100 ml of N, N-dimethylacetamide containing 17.2 g of sulfanilamide and 10 ml of pyridine. 36.6 g of amylphenoxy) hexanoyl chloride was added dropwise at 5 ° C. or lower over about 30 minutes. After completion of dropping, stirring was continued for 1 hour under ice cooling and 1 hour under water cooling. When 300 ml of water was added to this reaction mixture, a highly viscous oily substance was precipitated. The upper claw was removed by decanting, the oily substance was dissolved in 200 ml of ethyl acetate, and dried over anhydrous magnesium sulfate overnight. Magnesium sulfate was removed by filtration, and ethyl acetate was concentrated to dryness under reduced pressure. The residue was dissolved in 100 ml of methanol and 30 ml of water was added with stirring at room temperature. To this suspension, 0.1 g of K-12 seed crystals was added, and the precipitated crystals were collected by filtration and washed with water 100
It was washed with ml. The crude crystals were thoroughly dried and n-hexane 3 was added.
K by recrystallizing from 00 ml and 50 ml of ethyl acetate
21.0 g of -12 was obtained. mp 120 ° C.

(Synthesis Example 6) Synthesis of Exemplified Compound K-16 47 g of phenyl chloroformate was added to an internal temperature of 0 to 0 while stirring to a solution of 300 ml of N, N-dimethylacetamide containing 51.6 g of sulfanilamide and 30 ml of pyridine. 5 ° C
It was added dropwise over 30 minutes while maintaining the above. After completion of dropping, the mixture was further stirred at the same temperature for 1 hour and under water cooling for 1 hour. When 600 ml of water was added to this reaction mixture, white crystals were precipitated. After stirring for 1 hour as it was, the crystals were collected by filtration, washed with water and dried. Yield 15.0g mp111-112 ° C

The preferred amount of the compound represented by the general formula (III) used in the present invention is 0.1 per mol of the dye image-forming compound.
1 to 500 mol%, preferably 20 mol% to 300 mol
%, And more preferably 50 mol-200 mol%.
Further, the compound of the present invention is preferably added to the same layer as the dye image-forming compound. In the present invention, as a method for adding the dye image-forming compound to the hydrophilic colloid layer,
Various known methods can be used. Usually, it can be added by an oil-in-water dispersion method known as an oil protect method. That is, it is a method in which a dye image-forming compound is dissolved in a high-boiling point organic solvent such as a phosphoric acid ester or a phthalic acid ester and a low-boiling point auxiliary solvent, and then dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, an oil-in-water dispersion may be prepared by adding water or an aqueous gelatin solution to a solution of a dye image-forming compound containing a surfactant and causing phase inversion. In order to remove the low boiling point organic solvent from the resulting dispersion, it is also preferable to use a method such as distillation, noodle washing, or ultrafiltration. As a dispersion medium of such a dye image forming compound, a dielectric constant of 2 to 20 (25 ° C.),
High-boiling point organic solvents having a refractive index of 1.4 to 1.7 and / or columns 7 to 15 of US Pat. No. 4,857,449 and 12 to 30 of WO88 / 00723.
The water-insoluble polymer compounds described in page etc. can be preferably used. In the present invention, the weight ratio of the dispersion medium to the dye image-forming compound is preferably 0.1-10, more preferably 0.3-3. Next, the color diffusion transfer method of the present invention will be described. Film used for color diffusion transfer method
A typical form of the unit is a form in which the image receiving element and the photosensitive element are laminated on one transparent support, and it is not necessary to peel the photosensitive element from the image receiving element after the transfer image is completed. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer. A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye-donor substance for each emulsion layer, A combination of a magenta dye-donating substance and a cyan dye-donating substance (herein, "infrared light-sensitive emulsion layer" means an emulsion layer sensitive to light of 700 nm or more, especially 740 nm or more). ). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the dye-donating substance-containing layer so that the transferred image can be viewed through the transparent support.

A light shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development processing can be completed in a bright place. If desired, a peeling layer may be provided at an appropriate position so that all or part of the light-sensitive element can be peeled off from the image-receiving element (for example, such an embodiment is disclosed in JP-A-56-6
7840 and Canadian Patent 674,082).

As another embodiment of the laminate type which is peeled off, a layer having at least (a) a neutralizing function, (b) a dye image receiving layer, and (b) on a white support described in JP-A-63-226649. c) a release layer, (d) a light-sensitive element sequentially having at least one silver halide emulsion layer combined with a dye image-forming substance, an alkali processing composition containing a light-shielding agent, and a transparent cover sheet. There is a color diffusion transfer photographic film unit characterized by having a layer having a light shielding function on the side opposite to the side where the processing composition is developed.

In another form in which peeling is not necessary, the above-mentioned photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. .
U.S. Pat. No. 3,730,71 describes a mode in which an image receiving element, a white reflective layer, a peeling layer and a photosensitive element are laminated on the same support and the photosensitive element is intentionally peeled from the image receiving element.
No. 8.

On the other hand, there are roughly two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports, one is a peeling type and the other is a peeling-free type. is there. Explaining these in detail, in a preferred embodiment of the peelable film unit, at least one image receiving layer is coated on one support, and the photosensitive element is coated on a support having a light shielding layer. , The photosensitive layer coated surface and the mordant layer coated surface do not face each other before the exposure is completed, but after the exposure is completed (for example, during the development process), the photosensitive layer coated surface is turned over and overlapped with the image receiving layer coated surface. .
After the transfer image is completed on the mordant layer, the light-sensitive element is rapidly separated from the image-receiving element.

In a preferred embodiment of the peel-free type film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-shielding layer. However, the photosensitive layer coated surface and the mordant layer coated surface face each other and are superposed.

A pressure-rupturable container (processing element) containing an alkaline processing liquid may be combined with the above-described form. Among others, in a peel-free type film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. Further, in the form in which the light-sensitive element and the image-receiving element are separately coated on the two supports, it is preferable that the processing element is disposed between the light-sensitive element and the image-receiving element at the latest during the development processing. The processing element preferably contains a light-shielding agent (such as carbon black or a dye whose color changes with pH) and / or a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the color diffusion transfer type film unit, it is preferable that a neutralization timing mechanism composed of a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element or the photosensitive element.

The constituent elements included in the present invention will be sequentially described below. I. Photosensitive Sheet A) Support The support of the photosensitive sheet used in the present invention may be any smooth transparent support usually used for photographic light-sensitive materials, such as cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. It is preferable to provide an undercoat layer. The support usually contains a slight amount of a dye or a pigment such as titanium oxide in order to prevent light piping. The thickness of the support is 50
˜350 μm, preferably 70 to 210 μm, more preferably 80 to 150 μm. If necessary, a curl-balancing layer is provided on the back side of the support or JP-A No.
An oxygen barrier layer described in 6-78833 can be provided.

B) Image Receiving Layer The dye image receiving layer used in the present invention comprises a hydrophilic colloid containing a mordant. 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 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 and having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. It is a thing. The amount of mordant applied is generally 0.5.
10 to 10 g / m ^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 preferable. In the image receiving layer, the anti-fading agents described in JP-A-62-30620, JP-A-62-30621 and JP-A-62-215272 can be incorporated.

C) White Reflective Layer The white reflective layer forming the white background of the color image usually contains a white pigment and a hydrophilic binder. The white content for the white reflective layer includes 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. Further, these may be used alone or may be mixed and used within a range capable of obtaining a desired reflectance. A particularly useful white pigment is titanium dioxide. The whiteness of the white reflective layer is
Although it depends on the type of pigment, the mixing ratio of the pigment and the binder, and the coating amount of the pigment, the light reflectance is preferably 70% or more. Generally, the greater the amount of pigment applied, the better the whiteness, but as the imaging dye diffuses through this layer, the pigment resists the diffusion of the dye,
It is desirable to have an appropriate coating amount. Titanium dioxide 5
A white reflective layer having a light reflectance of 78 to 85% with light having a wavelength of 540 nm is preferred, which is applied to -40 g / m ² , preferably 10 to 25 g / m ² . Titanium dioxide can be selected from various commercially available brands and used. Among these, it is particularly preferable to use rutile type titanium dioxide. Most of the commercially available products are surface-treated with alumina, silica, zinc oxide or the like. In order to obtain a high reflectance, the surface treatment amount is preferably 5% or more. Examples of commercially available titanium dioxide include Ti-pure R93 manufactured by DuPont.
In addition to 1, there are those described in Research Disclosure No. 15162. As a binder for the white reflective layer, an alkali-permeable polymer matrix, for example, gelatin, polyvinyl alcohol, or a cellulose derivative such as hydroxyethyl cellulose or carboxymethyl cellulose can be used. A particularly preferred binder for the white reflective layer is gelatin. The ratio of white pigment to gelatin is
1/1 to 20/1 (weight ratio), preferably 5/1 to 10
It is / 1 (weight ratio). In the white reflective layer, Japanese Patent Publication Sho 62
It is preferable to incorporate an anti-fading agent such as -30620 and 62-30621.

D) Light-shielding layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the white reflective layer and the photosensitive layer. As the light shielding agent, any material having a light shielding function is used, but carbon black is preferably used. US Pat. No. 4,61
You may use the decomposable dye as described in 5,966.
The binder for coating the light-shielding agent may be any as long as it can disperse carbon black, and gelatin is preferable. Examples of carbon black raw materials include D
onnel Voet "Carbon Black" MarcelDekker, Inc. (1
Any method such as a channel method, a thermal method and a furnace method as described in 976) can be used. The particle size of carbon black is not particularly limited, but is preferably 90 to 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 optical density.

E) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming substance is provided above the light shielding layer. The constituent elements will be described below. (1) Dye image-forming substance Is the dye image-forming substance other than the general formula (I) used in the present invention a non-diffusible compound that releases a diffusible dye (may be a dye precursor) in association with the silver phenomenon? , Or the diffusivity of itself changes, and "Theory of the Photographic Process"
It is described in the 4th edition. All of these compounds can be represented by the following general formula (IV). Formula (IV) (DYE-Y) _n -Z {DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z represents an image-like structure. To produce a difference in the diffusivity of the compound represented by (DYE-Y) _n -Z corresponding to or opposite to the photosensitive silver salt having a latent image, or to release DYE and release the DYE. And (DYE-Y) _n -Z represent a group having a property of causing a difference in diffusibility, n represents 1 or 2, and when n is 2, two DYE-Y are the same. But it can be different. According to the function of Z, it is roughly classified into a negative type compound which becomes diffusive in the silver developed area and a positive type compound which becomes diffusible in the undeveloped area. Specific examples of the negative Z include those that are oxidized and cleaved to release a diffusible dye as a result of development. Specific examples of Z include U.S. Pat. Nos. 3,928,312, 3,993,638, 4,076,529, 4,152,153, 4,055,428 and 4,053. , 312, 4,198,235, 4,179,291, 4,149,892, 3,844,785, 3,443,943, 3,751,406. No. 3,443,939, No. 3,443,940, No. 3,628,952, No. 3,980,479, No. 4,183,753, No. 4,142,891, 4,278,750, 4,139,379, 4,218,368, 3,421,964, 4,199,355, 4,199,354, 4 , 135,929, 4,336,322, 4,139,389, HirakiAkira 53-50736 issue, same 51-104343 JP, same 54-130122 JP, the same 5
No. 3-110827, No. 56-12642, No. 56-
16131, 57-4043, 57-650.
No. 57-20735, No. 53-69033, No. 54-130927, No. 56-164342, No. 5
7-119345 and the like. For positive compounds, see Angevante Chemie International Edition English (Angev. Chem. Inst. E
d. Engl.), 22, 191 (1982). A specific example thereof is a compound (dye developing agent) which is initially diffusible under alkaline conditions but is oxidized by development to become non-diffusible. Typical examples of Z effective for this type of compound are those described in US Pat. No. 2,983,606. Further, as another type, a diffusible dye is released by self-ring closure under an alkaline condition, but the dye is substantially not released when oxidized by development. Z with such a function
For specific details of U.S. Pat. No. 3,980,479,
JP-A-53-69033, JP-A-54-130927,
US Patents 3,421,964 and 4,199,355
No. etc. Another type is one that does not itself release a dye but releases a dye when reduced. This type of compound can be used in combination with an electron donor to release the diffusible dye imagewise by reaction with the remaining electron donor which has been imagewise oxidized by silver development. Regarding the atomic group having such a function, for example, US Pat. Nos. 4,183,753 and 4,14
2,891, 4,278,750, 4,13
9,379, 4,218,368, JP-A-53-
110827, U.S. Pat. Nos. 4,278,750, 4,356,249, 4,358,525, Japanese Patent Laid-Open Nos. 53-110827, 54-130927, 56-164342, and Kokai Giho. No. 87-6199, European Patent Publication No. 220,746A2, and the like.
When this type of compound is used, it is preferably used in combination with a diffusion resistant electron donating compound (known as an ED compound) or its precursor. E
Examples of the D compound include, for example, US Pat. No. 4,263,39
3, 4,278,750, JP-A-56-1387.
No. 36 and the like. On the other hand, DY of the above general formula
Specific examples of the dye represented by E are described in the following documents, and can be used in combination with the compound of the general formula (I). Examples of yellow dyes: US 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, 4,336,322: JP-A-51-114930.
56-71072: Research Disclosure 1763.
No. 0 (1978) and No. 16475 (1977). Examples of magenta dyes: U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308 and 3,954. , 476, 4,233,237, 4,255,509, 4,250,246, 4,142,891, 4,207,104, 4,287,292. No .: JP-A-52-106727,
53-23628, 55-36804, 56
-73057, 56-71060, 55-13
What is described in No. 4. Examples of cyan dyes: US Pat. Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220 and 4,242. , 435, 4,142,891, 4,195,994, 4,147,544, 4,148,642; British Patent 1,551,138.
Nos. 54-99431 and 52-8827.
No. 53-47823, No. 53-143323, No. 5
4-99431, 56-71061; European Patents (EP) 53,037, 53,040; Rese
those described in arch Disclosure 17,630 (1978) and 16,475 (1977). These compounds are disclosed in JP-A-62-215272, 144-
It can be dispersed by the method described on page 146. Further, these dispersions include 137-JP-A-62-215272.
The compounds described on page 144 may be included.

(2) Silver Halide Emulsion The silver halide emulsion used in the present invention may be a negative type 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 a silver halide grain may be used. The internal latent image type direct positive emulsion includes, for example, a so-called “conversion type” emulsion formed by utilizing the difference in solubility of silver halide, or a metal ion doped or chemically sensitized, or both of them. There is a "core / shell type" emulsion in which at least a light-sensitive site of an inner core (core) grain of the applied silver halide is covered with an outer shell (shell) of silver halide. No. 592,250, No. 3,206,313
No., British Patent No. 1,027,146, US Patent No. 3,76
1,276, 3,935,014, 3,44
7,927, 2,297,875, 2,56
No. 3,785, No. 3,551,662, No. 4,39
5, 478, West German Patent 2,728,108, and U.S. Pat. No. 4,431,730. Also,
When an internal latent image type direct positive emulsion is used, it is necessary to provide surface fog nuclei by using light or a nucleating agent after imagewise exposure. As a nucleating agent therefor, US Pat.
3,785, 2,588,982 hydrazines, US Pat. No. 3,227,552 hydrazines, hydrazones, British Patent 1,283,
835, JP-A-52-69613, US Pat.
No. 15,615, No. 3,719,494, No. 3,73
4,738, 4,094,683, 4,11
Heterocyclic quaternary salt compounds described in US Pat. No. 5,122, sensitizing dyes having a nucleating substituent in the dye molecule described in US Pat. No. 3,718,470, US Pat.
30,925, 4,031,127, 4,24
No. 5,037, No. 4,255,511, No. 4,26
6,013, 4,276,364, British Patent 2,
Thiourea-bonding type acylhydrazine compounds described in, for example, US Pat. No. 4,080,270.
No. 4,278,748, British Patent No. 2,011,3
For example, an acylhydrazine-based compound having a thioamide ring described in 91B or the like and a heterocyclic group such as triazole or tetrazole bonded as an adsorptive group is used.

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

(3) Construction of Photosensitive Layer For the reproduction of natural colors by the subtractive color method, the above dye that provides a dye having a selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the above 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. 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
The partition layer described in No. 5267 can be provided to increase the color image density, and a reflective layer can be provided to increase the sensitivity of the photosensitive element. The reflective 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 amount of titanium oxide applied is 0.1 g / m ^{2 to} 8 g / m ² , preferably 0.1.
It is a ^{2g / m 2 ~4g / m 2} . Examples of the reflective layer are described in JP-A-60-91354. In a preferable 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. An arbitrary layer can be provided between each emulsion layer unit as needed. In order to prevent the unfavorable influence of the development effect of one emulsion layer on other emulsion layer units,
It is preferable to install an intermediate layer. When the 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 product of the developer. Specific examples thereof include non-diffusible hydroquinone, sulfonamide phenol, sulfonamide naphthol, and the like, and more specifically, JP-A-50-2.
1249, 50-23813, JP-A-49-10.
6329, 49-129535, U.S. Pat.
36,327, 2,360,290, 2,40
3,721, 2,544,640, 2,73
2,300, 2,782,659, 2,93
7,086, 3,637,393, 3,70
0,453, British Patent 557,750, JP-A-57.
No. 24941, No. 58-21249, and the like. Regarding the dispersion method thereof, JP-A-60-23
8831 and Japanese Examined Patent Publication No. 60-18978. When a compound capable of releasing a diffusible dye by silver ion as described in JP-B-55-7576 is used, it is preferable to include a compound for capturing silver ion in the intermediate layer. In the present invention, an irradiation prevention layer, a UV absorber layer, a protective layer and the like are coated as necessary.

F) Peeling Layer In the present invention, a peeling layer may be provided for peeling off the photosensitive sheet in the unit at any place after the treatment, if necessary. Therefore, this peeling layer must be easy to peel off after the treatment. Materials for this purpose include, for example, JP-A-47-8237, JP-A-59-220727 and JP-A-5-220727.
9-229555, 49-4653, U.S. Pat. Nos. 3,220,835, 4,359,518, JP-A-49-4334, 56-65133, 45-.
24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 4,401,746 and 4,366,227 can be used. One of the specific examples 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. Another example is 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, polyacrylate, polymethylmethacrylate, polybutylmethacrylate, or a copolymer thereof may be used. The release layer can be a single layer,
Further, for example, JP-A-59-220727 and JP-A-60-6.
It may be composed of a plurality of layers as described in No. 0642.

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

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

H) Layer Having Neutralizing Function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize the alkali carried in from the treatment composition, and is necessary. Accordingly, it may have a multi-layered structure including layers such as a neutralization rate adjusting layer (timing layer) and an adhesion enhancing layer. A 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 oleic acid described in US Pat. No. 2,983,606. Higher fatty acids such as US Pat. No. 3,362,819
Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides as disclosed in US Pat. No. 2,290,699; acrylic acid and acrylic acid as disclosed in French Patent 2,290,699 Ester isotopes;
No. 4,139,383 or Research Disclosure No. 16102 (19
Mention may be made of latex-type acidic polymers as disclosed in 77). Others, US Patent 4,08
No. 8,493, JP-A Nos. 52-153739 and 53-
No. 1023, No. 53-4540, No. 53-4541
The acidic substances disclosed in JP-A No. 53-4542 and the like can also be mentioned. Specific examples of acidic polymers 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, and acetate-hydrogenphthalate. The polymer acid can be used as a mixture with a hydrophilic polymer. As such a polymer,
Examples include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polymethyl vinyl ether and the like. Of these, polyvinyl alcohol is preferable. Further, the polymer acid is a polymer other than a hydrophilic polymer,
For example, cellulose acetate or the like may be mixed. 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 and 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. If too much or too little hydrophilic polymer is mixed, the quality of the photograph will be degraded. The weight ratio of hydrophilic polymer to polymeric acid is 0.1 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. In addition, if necessary, an antioxidant, a fluorescent brightening agent, a development inhibitor and a precursor thereof may be added. Timing layers used in combination with the neutralization layer include polymers that reduce alkali permeability such as gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like; A latex polymer produced by copolymerizing a small amount of a hydrophilic comonomer such as an acrylic acid monomer to increase the activation energy of alkali permeation; a polymer having a lactone ring is useful. Among them, JP-A-54-136328,
US Pat. Nos. 4,267,262 and 4,009,030
No. 4,029,849, and other timing layers using cellulose acetate; JP-A-54-128
No. 335, No. 56-69629, No. 57-6843.
U.S. Pat. Nos. 4,056,394 and 4,061,4
No. 96, No. 4,199,362, No. 4,250,24
No. 3, No. 4,256,827, No. 4,268,604
Latex polymers prepared by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid; disclosed in U.S. Pat. No. 4,229,516; polymers having a lactone ring disclosed in U.S. Pat. No. 4,229,516; -25735
Nos. 56-97346, 57-6842, European Patent (EP) 31,957A1, 37,72.
The polymers disclosed in 4A1 and 48412A1 are particularly useful. In addition, those described in the following documents can also be used. US Pat. Nos. 3,421,893, 3,455,686, 3,575,701, 3,778,265, 3,785,815, 3,847,615, and US Pat. 4,088,493, 4,123,275, 4,148,653, 4,201,587, 4,288,523, 4,297,431, West German patent application (OLS) 1,6
22,936, 2,162,277, Research D
isclosure 15162, No. 151 (1976).
The timing layer using these materials may be used alone or in combination of two or more layers. In addition, a timing layer made of these materials can be used, for example, in US Pat.
029, West German patent application (OLS) 2,913,164
No. 3,014,672, JP-A-54-15583.
No. 7, 55-138745, and the like, development inhibitors and / or their precursors, hydroquinone precursors, and other useful photographic additives disclosed in US Pat. No. 4,201,578. It is also possible to incorporate the precursor etc.
Further, as a layer having a neutralizing function, JP-A-63-1
Providing an auxiliary neutralization layer as described in JP-A-68648 and JP-A-63-168649 is effective in reducing a change in transfer density with time after the treatment.

I) Others In addition to the layer having a neutralizing function, a back layer, a protective layer, a filter dye layer and the like may be provided as a layer having an auxiliary function. The back layer is provided for adjusting curl and imparting slipperiness. Filter dyes may be added to this layer. The protective layer is mainly used to prevent adhesion to the back surface of the cover sheet and adhesion to the protective layer of the photosensitive material when the photosensitive material and the cover sheet are superposed. The cover sheet may contain a dye to adjust the sensitivity of the photosensitive layer. The filter dye is directly in the support of the cover sheet or a layer having a neutralizing function, further the back layer,
It may be added to the protective layer, the capture mordant layer or the like, or a single layer may be provided.

III. Alkali Processing Composition The processing composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element and placed on the back surface of the support or on the side of the photosensitive layer opposite to the processing solution. It forms a pair with a light-shielding layer to completely shield the photosensitive layer from external light, and at the same time, develops the photosensitive layer with the components contained therein. Therefore, in the composition, an alkali, a thickener, a light-shielding agent, a developing agent, and further, a development accelerator for controlling the development, a development inhibitor, and an antioxidant for preventing the deterioration of the developing agent. Contains etc. A sunscreen is always included in the composition. 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), alkali metal phosphates (eg potassium phosphate). Examples thereof include guanidines and quaternary amine hydroxides (eg, tetramethylammonium hydroxide), but potassium hydroxide and sodium hydroxide are preferred. The thickener is necessary for uniformly developing the processing liquid and for maintaining the close contact between the photosensitive layer and the cover sheet. For example, an alkali metal salt of polyvinyl alcohol, hydroxyethyl cellulose or carboxymethyl cellulose is used, and preferably hydroxyethyl cellulose or sodium carboxymethyl cellulose is used. As the light-shielding agent, any dye or 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. As the preferred developing agent, any developing agent can be used as long as it cross-oxidizes the dye image-forming substance and does not substantially cause stain when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor type. These developers may be included in the appropriate layers of the light sensitive element or in the alkaline processing liquid. Specific examples of the compound include aminophenols and pyrazolidinones. Of these, 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. JP-A-62-215272 7 for either photosensitive sheet, cover sheet or alkaline processing composition
2-91, development accelerators, 146-155, hardeners, 201-210, surfactants 210
Fluorine-containing compounds described on page 222, thickeners described on pages 225 to 227, antistatic agents described on pages 227 to 230, 230
The polymer latex described on page 239 to the matting agent described on page 240 may be included. Further, it is desirable that these alkaline liquid compositions are transferred onto the photosensitive material at a developed thickness (processing liquid amount per m ² after transferring the processing liquid) of 20 to 200 μ. The processing temperature for processing a light-sensitive material containing the compound of general formula (I) is preferably 0 to 50 ° C., and 0 to 50 ° C.
40 ° C. is more preferable.

[0082]

The present invention is described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 A comparative photosensitive material 101 was prepared by coating a 150 μm transparent polyethylene terephthalate film support in a layer structure as shown in Table 3.

[0084]

[Table 5]

[0085]

[Table 6]

[0086]

[Table 7]

[0087]

[Table 8]

[0088]

[Chemical 25]

[0089]

[Chemical formula 26]

[0090]

[Chemical 27]

[0091]

[Chemical 28]

[0092]

[Chemical 29]

Then, in the 16th layer (yellow color material layer),
The same light-sensitive material was prepared except that the yellow coloring material shown in Table 2 and the compound represented by the general formula (II) were coated so as to have a concentration of 0.54 mmol / m ² . The cover sheet was created as follows. The following layers were coated on a polyethylene terephthalate transparent support containing a gelatin-primed anti-light piping dye. (1) 10.4 g / m ^{2 of} an acrylic acid / butyl acrylate (molar ratio 8: 2) copolymer having an average molecular weight of 50,000 and 1,
4-bis (2,3-epoxypropoxy) -butane 0.
Neutralization layer containing 1 g / m ² . (2) Acetyl cellulose with an acetylation degree of 51% 4.3 g / m ² ,
A neutralization timing layer containing 0.2 g / m ² of poly (methyl vinyl ether-co-monomethyl maleide). (3) Styrene / butyl acrylate / acrylic acid-N-
Methylol acrylamide weight ratio 49.7 / 42.3
The polymer latex emulsion-polymerized at a ratio of / 4/4 and the polymer latex emulsion-polymerized at a weight ratio of methyl methacrylate / acrylic acid / N-methylol acrylamide of 93: 3: 4 have a solid content ratio of 6: 4. Blended so that the total solid content is 1.0 g / m ² .

The formulation of the alkaline treatment composition is shown below.
0.8 g of the treatment liquid having the following composition was filled in a destructible container. 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10.0 g methylhydroquinone 0.18 g 5-methylbenzotriazole 3.0 g sodium sulfite (anhydrous) 0.2 g benzyl alcohol 1.5 cc Carboxymethyl cellulose Na salt 58 g Carbon black 150 g Potassium hydroxide (28% aqueous solution) 200 cc Water 680 cc Each of 0.8 g of the treatment liquid having the above composition was filled in a “pressure rupturable container”. The light-sensitive material was exposed from the emulsion layer side through a gray filter, then overlapped with the cover sheet, and the processing solution was developed between the two materials at 25 ° C. using a pressure roller so that the thickness of the material was 75 μm. The transfer property was determined by measuring the yellow reflection density 2 minutes after the treatment.
As for sharpness, after processing, 40 ° C-70% RH
C. after standing under for 7 days T. F. Was measured and the spatial frequency at the point giving CTF = 0.5 was determined for convenience.
The results are shown in Table 4.

[0095]

[Table 9]

As is clear from Table 4, when the yellow coloring material of the present invention is used, the transfer density is high and the sharpness is improved. This effect was particularly remarkable when the additive represented by the general formula (III) of the present invention was used.

Example 2 A comparative photosensitive element (301) having the following constitution was prepared.

Photosensitive Element 301 A photosensitive sheet was prepared by coating the following layers on a polyethylene terephthalate transparent support as follows.

Back layer: (a) Carbon black 4.0
A light-shielding layer having g / m ² and gelatin 2.0 g / m ² .

Emulsion layer side: (1) The following cyan dye-releasing redox compound 0.44 g / m ² , tricyclohexyl phosphate 0.09 g / m ² , 2,5-di-t-pentadecylhydroquinone 0.008 g / m ² . ² , and a layer containing 0.8 g / m ² of gelatin.

[0101]

[Chemical 30]

(2) A layer containing 0.5 g / m ² of gelatin. (3) Red sensitive inner latent type direct positive silver bromide emulsion.
6 g / m ² ), gelatin 1.2 g / m ² , the following nucleating agent:
015g / m ² and red-sensitive emulsion layer containing a 2-sulfo -5-n-pentadecylhydroquinone sodium salt 0.06 g / m ^2.

[0103]

[Chemical 31]

[0104] (4) 2,5-di -t- pentadecylhydroquinone 0.43 g / m ^2, trihexyl phosphate 0.1 g / m ^2, and a layer containing gelatin 0.4 g / m ^2. (5) The following magenta dye-releasing redox compound was added to the following:
3 g / m ² , tricyclohexyl phosphate (0.08
g / m ² ), 2,5-di-tert-pentadecylhydroquinone (0.009 g / m ² ) and gelatin (0.5 g / m ² ).
a layer containing m ² ).

[0105]

[Chemical 32]

(6) Green-sensitive inner latent type direct positive silver bromide emulsion (0.42 g / m ^{2 in} silver amount), gelatin (0.9 g / m ² ).
m ² ), the same nucleating agent as layer (3) (0.013 mg / m ² ) and 2-sulfo-5-n-pentadecylhydroquinone.
A green-sensitive emulsion layer containing a sodium salt (0.07 g / m ² ).

(7) The same layer as (4). (8) yellow dye-releasing redox compound having the following structure (0.53 g / m ^2), tri-cyclohexyl phosphate (0.13g / m ^2), 2,5- di -t- pentadecylhydroquinone (0.014 g / m ² ) And gelatin (0.7 g / m ² ).

[0108]

[Chemical 33]

(9) Blue-sensitive inner latent type direct positive silver bromide emulsion (0.6 g / m ^{2 in} silver amount), gelatin (1.1 g / m ² ).
m ² ), the same nucleating agent (0.019 mg / m ² ) as in layer (3) and 2-sulfo-5-n-pentadecylhydroquinone.
Blue-sensitive emulsion layer containing sodium salt (0.05 g / m ² ). (10) A layer containing 1.0 g / m ² of gelatin.

Then, a similar light-sensitive material was prepared except that the compound of the present invention was added to the cyan-, magenta-, and yellow-dye-releasing redox compound-containing layer of the above light-sensitive material as shown in Table 5 in an amount of 100 mol%. Dye Image Receiving Sheet An image receiving sheet having the layer constitution shown in Table 5 was prepared.

[0111]

[Table 10]

[0112]

[Chemical 34]

Treatment liquid 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 6.9 g Methylhydroquinone 0.3 g 5-Methylbenzotriazole 3.5 g Sodium sulfite (anhydrous) 0.2 g Carboxymethyl cellulose / Na salt 58 g Potassium hydroxide (28% aqueous solution) 200 cc Benzyl alcohol 1.5 cc Water 835 cc Then, the photosensitive sheet was imagewise exposed, and then the image-receiving sheet and the photosensitive sheet were superposed on each other. The treatment liquid was treated between the sheets to a thickness of 60 μm. Treatment is 25 ℃
The maximum density (Dmax) when the photosensitive sheet and the image receiving sheet were peeled off was examined 60 seconds after the treatment. The results are shown in Table 6.

[0114]

[Table 11]

As is clear from Table 6, when the yellow coloring material of the present invention is used, good transferability is exhibited.

Example 3 The yellow dyes (D1 to D6) of the present invention were mixed at pH = 11.0.
Was dissolved in an alkaline solution of and was coated on a polyethylene terephthalate film support so as to have the following layer structure. (Yellow dye layer) Yellow dye 0.50 mmol / m ² Gelatin 0.2 g / m ² Then, the above-mentioned coating material was used as the photosensitive material 10 prepared in Example 1.
0.8 g of each of the following treatment liquids was filled in a “pressure rupturable container” and treated at 25 ° C. using a pressure roller so that a thickness of 75 μm was formed between both materials. Treatment liquid Sodium sulfite 0.2 g Benzyl alcohol 1.5 cc Carboxymethyl cellulose Na salt 58 g Potassium hydroxide (28% aqueous solution) 200 cc Water 830 cc The transferability was evaluated at the time of giving half the yellow density for 20 minutes after the treatment. The results are shown in Table 7.

[0117]

[Table 12]

As is clear from Table 7, transferability is improved when the yellow dye of the present invention is used.

[0119]

INDUSTRIAL APPLICABILITY A light-sensitive material containing a compound represented by the general formula (I) (especially a light-sensitive material for color diffusion transfer has a high transfer speed, an excellent sharpness, a high transfer density and a high dye fastness. An image can be obtained, and an image with less stain and hue change can be obtained.

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[Procedure amendment]

[Submission date] August 24, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

Arylthio groups (phenylthio, 4-ethoxyphenylthio, etc.), alkoxycarbonyl groups (ethoxycarbonyl, hexadecyloxycarbonyl, 2-
Hexyldecyloxycarbonyl, etc.), carbamoyl group (dimethylcarbamoyl, 3-phenoxypropylcarbamoyl, dioctylcarbamoyl, etc.), sulfamoyl group (dimethylsulfamoyl, morpholinosulfonyl, dioctylsulfamoyl, hexadecylsulfamoyl, etc.), acyl group (Propionyl, benzoyl, etc.), sulfonyl group (methanesulfonyl, dodecylsulfonyl, etc.), urethane group (hexadecylurethane, 2-
Hexyldecyl urethane, etc.), amino group (dioctylamino, N-ethyl-N-dodecylamino, 4-methoxyanilino, etc.), sulfamoylamino group (3,3-dioctylaminosulfamoyl, butylaminosulfamoyl) Etc.), heterocyclic (α-pyridyl, 2-furfuryl, etc.), hydroxyl group, phosphonic acid ester group (dicyclohexylphosphonic acid ester, di-n-octylphosphonic acid ester, etc.).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

A preferred example of the compound represented by the general formula (III) is a diffusion resistant compound. The diffusion-resistant compound is a compound having a group in the molecule that sufficiently increases the molecular weight in order to immobilize it in the layer to which the molecule is added. Usually, an alkyl group having a total carbon number of 8 to 30, preferably 10 to 22, or an aryl group having a substituent having a total carbon number of 4 to 20 is used, and a plurality of these diffusion resistant groups may be contained. .

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

Preferred among these Y's are an alkyl group having 10 to 22 carbon atoms, an alkoxy group having 10 to 22 carbon atoms, an alkoxycarbonyl group having 10 to 30 carbon atoms, an acylamino group having 10 to 30 carbon atoms, Examples thereof include urethane groups having 10 to 30 carbon atoms.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

[0040]

[Chemical 18]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

[0041]

[Chemical 19]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

The compound of the present invention is preferably added to the same layer as the dye image forming compound. In the present invention, various known methods can be used as a method for adding the dye image-forming compound to the hydrophilic colloid layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protect method. That is, it is a method in which a dye image-forming compound is dissolved in a high-boiling point organic solvent such as a phosphoric acid ester or a phthalic acid ester and a low-boiling point auxiliary solvent, and then dispersed in a gelatin aqueous solution containing a surfactant. Alternatively,
Water or a gelatin aqueous solution may be added to a dye image forming compound solution containing a surfactant to form an oil-in-water dispersion with phase inversion. In order to remove the low boiling point organic solvent from the resulting dispersion, it is also preferable to use a method such as distillation, noodle washing, or ultrafiltration. As a dispersion medium of such a dye image forming compound, a dielectric constant of 2 to 20
(25 ° C.), a high boiling point organic solvent having a refractive index of 1.4 to 1.7 and / or No. 7 of U.S. Pat. No. 4,857,449.
To column 15 and pages 12 to 30 of WO88 / 00723, etc. can be preferably used. In the present invention, the weight ratio of the dispersion medium to the dye image forming compound is preferably 0.1 to 10,
It is more preferably 0.3 to 3. Next, the color diffusion transfer method of the present invention will be described. A typical form of a film unit used in the color diffusion transfer method is that an image receiving element and a photosensitive element are laminated on one transparent support, and the photosensitive element is peeled from the image receiving element after completion of a transfer image. It is an unnecessary form. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer. , A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a blue-sensitive emulsion layer,
A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a combination of a yellow dye-donor substance, a magenta dye-donor substance and a cyan dye-donor substance in each of the above emulsion layers (here, "Infrared light sensitive emulsion layer" is 70
An emulsion layer sensitive to light of 0 nm or more, particularly 740 nm or more). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the dye-donating substance-containing layer so that the transferred image can be viewed through the transparent support.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideaki Naruse 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. (72) Inventor Hiroshi Iwanaga 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (5)

[Claims] 1. A silver halide light-sensitive material comprising a compound represented by the following general formula (I). [Chemical 1] (In the formula, R ¹ represents an alkyl group, R ² represents an alkyl group,
It represents a cycloalkyl group, an aralkyl group or an aryl group. X is a hydrogen atom or R ³ SO ₂ - represents a group. R
³ represents an alkyl group having 1 to 3 carbon atoms. ) 2. A dye-releasing redox compound represented by the general formula (I) according to claim 1. 3. A silver halide light-sensitive material characterized by using a dye represented by the following general formula (II) for image formation. [Chemical 2] (In the formula, X has the same meaning as in formula (I).) 4. A dye represented by the general formula (II) according to claim 3. 5. A photosensitive material according to claim 1, which contains at least one compound represented by the general formula (I) according to claim 1 and at least one compound represented by the following general formula (III). . [Chemical 3] In the formula, Y is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonylamino group, a ureido group, an alkylthio group, an arylthio group, Alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, urethane group, amino group, sulfamoylamino group,
It represents a cyano group, a hydroxyl group, a phosphonate group or a heterocyclic group, and n represents an integer of 1 to 5. n
Is 2, 3, 4 or 5, Y may be the same or different. When n is 2, 3, 4 or 5, two Y's may combine with each other to form a saturated or unsaturated ring. Further, the above substituents may be substituted with other substituents.