JP2670913B2 - Color diffusion transfer photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color diffusion transfer light-sensitive material, and more particularly, to a diffusion-resistant compound which releases a diffusible dye in response to a reaction in which silver halide is reduced to silver. And a conventional negative-working silver halide emulsion to form a positive image. More specifically, it relates to a color diffusion transfer light-sensitive material that forms the above-mentioned positive image with high sensitivity and low minimum density.

[0002]

2. Description of the Related Art As a method for directly forming a positive image by a color diffusion transfer method, A) a direct positive silver halide emulsion and a diffusible dye corresponding to a reaction in which silver halide is reduced to silver are used. A method of using a combination of a diffusion-resistant compound (referred to as a negative dye-donor compound) to be released, and B).
Diffusion resistant compounds or silver halides that become diffusive in response to ordinary silver halide emulsions (negative-positive response silver halide emulsions) and silver halide reduction reactions There is a method of using a combination of diffusion-resistant compounds (which are referred to as positive dye-donor compounds) that release diffusible dyes corresponding to the reaction of being reduced to silver. In the method of A), for example, British Patent No. 1,330,524
No. 48-39165, U.S. Pat. No. 3,44
No. 3,940, No. 4,474,867, No. 4,48
No. 3,914, etc., a compound having a diffusible dye as a leaving group and releasing the diffusible dye by a coupling reaction with an oxidized form of a reducing agent (DDR coupler), US Pat. 3,928,312, 4,0
53,312, 4,055,428, 4,33
A compound (DRR compound) described in No. 6,322, which is reducing to silver halide and releases a diffusible dye when silver halide is reduced is used. In the method of B), U.S. Pat. No. 3,134,764 is used.
No. 3,362,819, No. 3,597,200
No. 3,544,545, No. 3,482,972, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked (this dye developer is diffusible in an alkaline environment. However, it becomes non-diffusible when reacted with silver halide), U.S. Pat. No. 4,503,1
No. 37, etc., U.S. Pat. No. 3,980,479, which discloses a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide.
Releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat. No. 4,199,354 and releasing a diffusible dye by an intramolecular rewinding reaction of an isoxazolone ring described in U.S. Pat. No. 4,199,354. Compounds, US Pat. No. 4,559,290, European Patent 220,746A2
U.S. Pat. No. 4,783,396, Technical Report 87-
For example, a non-diffusible compound described in No. 6199 that releases a diffusible dye by reacting with a reducing agent remaining without being oxidized by development is used.

Among the above-mentioned two methods, the method B) is preferable in that high sensitivity can be easily obtained. However, the method B) has a problem that it is difficult to reduce the density of the lowest density portion which is particularly important in image formation. In the method B), the dye-releasing reaction between the reducible dye-donor compound and the electron donor and the oxidation reaction of the electron donor by the oxidant of the electron transfer agent (generated by the development of the photosensitive silver halide). The competitive reaction determines the density of the lowest density area (corresponding to the high exposure area) of the positive image. Therefore, in order to reduce the minimum density at a high density, there is required a technique for controlling the development of the photosensitive silver halide and optimizing the production of the oxidant of the electron transfer agent.

On the other hand, it is used for silver halide photographic light-sensitive materials.
Various types of silver halide grains are known.
However, tabular grains are known as one of them. Flat plate
Already described in US Pat.
No. 434, 226, No. 4,439, 520, No. 4, 4
No. 14,310, No. 4,433,048, No. 4,41
4,306, 4,459,353, JP-A-59-
No. 99433, No. 62-209445, etc.
And the technology of use are disclosed, and color sensitization by a sensitizing dye is disclosed.
Improved sensitivity, including improved efficiency, improved sensitivity / granularity relationship
Sharpness due to the unique optical properties of tabular grains
Known benefits such as improved
Have been. The present invention is directed to the transfer within the major surface of tabular silver halide.
The technology to control the position. Silver halide crystals
For the rearrangement of C. R. Berry, J.M. Appl. Phys. ,
27 , 636 (1956), C.I. R. Berry, D.M. C. Skillman,
J. Appl. Phys. , 35 , 2165 (196
4), J. F. Hamilton, Photo. Sci. E
ng. , 11 57 (1967), T.S. Shiozawa, J .; Soc. Photo. S
ci. Jap. , 34 16 (1971), T.W. Shiozawa, J .; Soc. Photo. S
ci. Jap. , 35 , 213, (1972), etc., including X-ray diffraction method or low-temperature transmission electron microscope.
It is possible to observe dislocations in crystals by the microscopic method
And straining the crystal
It is described that dislocations occur. On the other hand, of dislocation
The effects on photographic performance include G.I. C. Famel
1, R.I. B. Flint & J. B. Chante
r, J. et al. Photo. Sci. , 13 , 25 (1965)
There is a document on this, and a large size high aspect ratio plate-like odor
Where latent image nuclei are formed in silver halide grains and defects in the grains
It has been shown that the pits are closely related. JP 63
-220238, JP-A-1-201649, dislocation
Of tabular silver halide grains with intentionally introduced
It is shown. Tabular grains containing dislocations have no dislocations
Compared with tabular grains, the photographic characteristics such as sensitivity and reciprocity law
Excellent and sharpness and graininess when used in light-sensitive materials
Has been shown to be excellent. But with these particles
Dislocation lines are randomly introduced at the edges of tabular grains.
The number of dislocations also differs from grain to grain.

[0005]

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

[0006]

The above object is to provide a support having at least one photosensitive silver halide emulsion layer in combination with a dye image-forming material and an electron donor, the dye image-forming material comprising: Halogen consisting of at least one reducible dye-providing compound represented by the following general formula (I) that releases a diffusible dye when reduced, and is contained in at least one emulsion layer of the silver halide emulsion layer. At least 50% of the total projected area of the silver halide emulsion grains has an average grain diameter of 0.
The tabular grains are occupied by tabular silver halide grains having an average grain thickness of 3 μm or more and an average grain thickness of less than 0.5 μm and an average grain diameter / average grain thickness ratio of 2 or more, and the tabular grains are opposed to each other in parallel. This is achieved by a color diffusion transfer light-sensitive material characterized in that the major surface thereof is composed of (111) planes, and at least 30% of the tabular grains have dislocations on the major surface thereof. General formula (I) PWR- (Time) _t -Dye In the formula, PWR is reduced to give-(Tim).
e) represents a group that releases _t- Dye. Time is PWR
Represents a group that is released as-(Time) _t -Dye and then releases Dye through a subsequent reaction. t is 0
Or represents an integer of 1. Dye represents a dye or its precursor. Further, the above problem is that at least 50% of the total projected area of silver halide emulsion grains contained in at least one of the silver halide emulsion layers has an average grain diameter of 0.3 μm.
It is more preferably achieved by a color diffusion transfer light-sensitive material characterized by having an average particle thickness of m or more and an average particle thickness of less than 0.5 μm and an average particle diameter / average particle thickness ratio of 5 or more.

Hereinafter, the present invention will be described in detail. One of the characteristics of the present invention is to use a silver halide emulsion containing the above-defined grains, that is, tabular silver halide grains (hereinafter referred to as "tabular grains"). A tabular grain has two parallel or nearly parallel principal planes facing each other, and the diameter of a circle equivalent to the principal plane (diameter of a circle having the same projected area as the principal plane) is the distance between the principal planes (that is, grain thickness). Particle size of 2 times or more. The ratio of the average grain diameter to the average grain thickness (hereinafter referred to as grain diameter / thickness) of the emulsion containing tabular grains of the present invention is 2 or more, preferably 3 to 12, and particularly 5 to 10. Is preferred. Here, the grain diameter / thickness can be obtained by averaging the grain diameters / thicknesses of all tabular grains, but as a simple method,
It can also be determined as the ratio of the average diameter of all tabular grains to the average thickness of all tabular grains.

The diameter (corresponding to a circle) of the tabular grains of the present invention is 0.
3 μm or more, preferably 0.3 to 10 μm, more preferably 0.5 to 5.0 μm, and further preferably 0.5 to
2.0 μm. The particle thickness is less than 0.5 μm, preferably 0.05 to 0.4 μm, more preferably 0.08.
０．３0.3 μm. In the present invention, the tabular grains account for 50% of the total projected area of grains in the emulsion containing them.
Account for the above. It is preferably 70% or more, more preferably 90% or more. In the present invention, the particle diameter and the particle thickness can be measured by an electron micrograph of the particles as in the method described in US Pat. No. 4,434,226. Specific examples of the halogen composition of tabular grains include silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, and silver chloroiodobromide. Or silver chlorobromide is preferred. Further, silver thiocyanate, silver cyanate and the like may be contained.

Further, the tabular emulsion of the present invention has dislocations.
The dislocations of tabular grains are described, for example, in J. F. Hamilt
on, Photo. Sci. Eng. , 11 , 57 (19
67) and T.W. Shiozawa, J .; Soc. Pho
t. Sci. Japan, 35 , 213, (1972)
Can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, silver halide grains taken out under safety light are placed on a mesh for electron microscopic observation, taking care not to apply pressure that causes dislocation to the grains from the emulsion, to prevent damage (printout, etc.) by electron beams. The observation is performed by the transmission method in a state where the sample is cooled as described above. In this case, the thicker the particles, the more difficult it is for an electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μm). . From the photographs of the particles obtained by such a method, the dislocation position of each particle when viewed from the direction perpendicular to the main plane can be determined.

The dislocations present in the silver halide grains of the present invention are present in the main surface area of tabular grains. The main surface area of the tabular grains means an area having a certain thickness including the outer surfaces of opposing (111) planes. That is,
The tabular grains used in the present invention are tabular grains in which dislocations are present in the main surface region of the main surface excluding the edge portion. The edge part here means a circle having the same area as the main surface,
It refers to a region having the thickness of a tabular grain, which is present in the periphery of the tabular grain and has an area corresponding to an annular region that is 5% radially inward from the circumference and is in the center side. The central region of a tabular grain is the radius of a circle having the same area as the major surface of the grain and is 10
%, And has a thickness of tabular grains in a circular portion having a common center. The dislocation of the present invention is not localized at a specific position in a region including the main surface of the host particle, such as the edge portion and the central region described above.

The feature of tabular grains is that the area of the main surface is large with respect to the grain volume, and the introduction of dislocations into the large main surface region maximizes the merit of the tabular grains. . In the present invention, the ratio of the area of the main surface where dislocations are present to the total main surface area is at least 10% to 100%, preferably 20% to 100%, more preferably 30 to 100%.

Next, the method for producing the tabular grains of the present invention will be described. The tabular grains of the present invention are prepared by preparing tabular grains as a base (hereinafter, also referred to as "base grains" or "host grains"), a large number of fine silver chloride or salt odors on the main surface of the tabular grains as a base. It is prepared by four processes: generation of epitaxy of silver halide, physical ripening of a large number of minute epitaxies on main surfaces of tabular grains and / or conversion by halogen, and growth of dislocation by formation of silver halide shell. Since the rearrangement is generated at the place where the minute silver chloride or silver chlorobromide epitaxy is attached, the place where the dislocation exists is determined by controlling the place where the minute epitaxy is generated. The halogen composition of the base grain is silver bromide,
It may be any of silver iodobromide, silver chlorobromide and silver chloroiodobromide, but silver bromide is preferred. Regarding the tabular silver halide grains as the base, U.S. Pat. Nos. 4,434,226, 4,
439,520, 4,414,310, 4,4
33,048, 4,414,306, 4,45
No. 9,353 and the like disclose its manufacturing method and use technique.

In forming the base grains, tabular grains are preferably formed by adding fine silver halide grains instead of adding the silver salt aqueous solution and the halide aqueous solution to the reaction vessel holding the protective colloid aqueous solution. According to this method, the increase in grain thickness during tabular grain growth is very small.
This method is described in U.S. Pat. No. 4,879,208.
JP-A-1-183644, JP-A-2-44335,
The technology is disclosed in JP-A-2-43535 and JP-A-2-68538.

Further, the tabular grains that form the basis of the present invention are preferably monodisperse. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A No. 63-151618. Briefly describing the shape, 70% or more of the total projected area of silver halide grains is the minimum. It is occupied by a tabular silver halide having a hexagonal shape in which the ratio of the side having the maximum length to the length of the side having the length is 2 or less and having two parallel parallel surfaces as outer surfaces. ,
Furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains [the value obtained by dividing the variation (standard deviation) of the grain size represented by the circle-converted diameter of the projected area by the average grain size] is 20% or less. It has the monodispersity of.

Using these as host grains, silver chloride or silver chlorobromide is deposited as a large number of minute epitaxies on the main surface of the host grains. Specifically, silver potential (using the reference electrode as a saturated calomel electrode) +30 mV to +300 m
At V, preferably +50 mV to +250 mV, an aqueous silver salt solution and an aqueous halide solution (chloride or a mixture of chloride and bromide) are added to a reaction vessel holding the host emulsion. The temperature of the reaction vessel is 70 ° C to 30 ° C, preferably 60 ° C to 35 ° C, more preferably 50 ° C to 35 ° C. The amount of silver salt (mainly silver nitrate) and halide added is 0.1 to 30 mol% of the host grains, preferably 0.5 to 2
It is 0 mol%, more preferably 1 to 10 mol%. The size and number of the generated epitaxy depend on the conditions for forming the epitaxy and the halogen composition of the host grain, but the size of the epitaxy can be confirmed by a replica electron microscope photograph, and the average projected area diameter of the epitaxy is 0.15 μm. The number is 10 to 10,000
Particles / μm ² are present on the main surface of the host particles.

Next, physical aging of the epitaxy on the main surface of the host particles and / or conversion with halogen are performed. When physical ripening is performed, the minute epitaxy collapses,
It becomes larger hills, but dislocation lines are considered to be introduced at this time. The temperature for physical aging is 40 ° C
To 90 ° C, preferably 50 ° C to 90 ° C, more preferably 60 ° C to 80 ° C.

Halogen conversion is the replacement of a halogen forming a silver halide crystal with a different halogen, but a silver halide having a smaller solubility product than the silver halide existing as a crystal is formed. The conversion is initiated by the addition of halogen and also begins with the portion of the silver halide having greater solubility. Therefore, the halogen for performing the halogen conversion is arbitrary as long as the halogen has a composition such that the silver halide has a lower solubility than the silver halide epitaxially grown.
The amount of halogen added is preferably 5 to 100 mol%, and more preferably 10 to the amount of epitaxially grown silver.
~ 50 mol%. The halogen used is iodide, a combination of iodide and bromide, or bromide, and is added as an aqueous solution thereof. As a method of adding these halogens, it is preferable to add them as fine particles of silver iodide, silver iodobromide, or silver bromide. The size of the fine particles is preferably 0.1 μm or less, preferably 0.06 μm or less, and it is possible to prepare a fine particle emulsion in advance with these fine particles, but it is also disclosed in US Pat. No. 4,879,208. According to the method, it is preferable to supply these silver halide fine particles from a mixer.

Next, dislocation growth due to shell formation will be described. Dislocations are introduced by physical ripening and / or halogen conversion of microepitaxy formed on the main surface of the host tabular grains, and thereafter, when a silver salt aqueous solution and a halide aqueous solution are further added to form a shell, the dislocation is accompanied by the shell formation. Grow up. The amount of the shell may be 5 mol% or more in terms of silver amount with respect to the host particles. The halogen composition of the shell is arbitrary, and may be any of silver chloride, silver bromide, silver iodobromide, silver chloroiodobromide, and silver chlorobromide. As the method for forming the shell, the manufacturing method of the base tabular grains described above is directly applied. US Pat. No. 4,43
No. 4,226, No. 4,439,520, No. 4,41
No. 4,310, No. 4,433,048, No. 4,41
No. 4,306, No. 4,459,353 and the like disclose the production method and use technique. Further, in forming a shell, tabular grains can be formed by adding silver halide fine particles instead of adding a silver salt aqueous solution and a halide aqueous solution to a reaction vessel holding a protective colloid aqueous solution,
This method is described in U.S. Pat. No. 4,879,208.
JP-A-1-183644, JP-A-2-44335,
The technology is disclosed in JP-A-2-43535 and JP-A-2-68538.

Thus, according to the present invention, dislocations can be introduced into a selected area on the main surface of the tabular silver halide grain or the whole main surface. Regarding the distribution of dislocations in the depth direction introduced by the present invention, the starting point of the dislocations is
It is the main surface of the host tabular grain, and the dislocation reaches the surface of the shell by the subsequent shell formation. Therefore, the dislocations of the present invention exist between the main surface of the host and the surface of the shell, and they are disclosed in JP-A-63-220238 and JP-A-1-20.
It is quite different from the dislocation disclosed in 1649. That is, the dislocations disclosed in these two patents are introduced near the edge of the tabular grains, and are completely different from the dislocations of the present invention in their substance and distribution.

The dislocations in the present invention can be easily confirmed by observing a transmission image of silver halide tabular grains with a transmission electron microscope. For example, F. Hami
Lton, "Photographic Science and Engineering", Vol. 11, 1967, page 57, and Takeshi Shiozawa, "Journal of the Photographic Society of Japan," Vol. 35, No. 4, 1972,
It can be observed by a direct method using a transmission electron microscope at low temperature described on page 213. That is, the silver halide grains taken out under safe light are placed on a mesh for electron microscopic observation so that the emulsion grains are not printed out, and the sample is treated with liquid nitrogen or liquid helium to prevent damage by electron beams (such as printout). Observation is performed by a transmission method in a state of cooling. Here, the higher the accelerating voltage of the electron microscope, the clearer the transmission image can be obtained, but the particle thickness is 0.2.
200 KV is preferable up to 5 μm, and 1000 KV is preferable for grain thickness of more than 5 μm. The higher the accelerating voltage, the greater the damage of the particles by the irradiation electron beam. Therefore, it is desirable to cool the sample with liquid helium rather than liquid nitrogen. The photographing magnification can be appropriately changed depending on the particle size of the sample, but is 20,000 to 40,000.

The size of the tabular grains can be adjusted by controlling the temperature, selecting the kind and amount of the solvent, and the addition rate of silver salt and halide used during grain growth.

The grain surface of the emulsion containing tabular grains of the present invention is chemically sensitized. The above-mentioned chemical sensitization is described by James, The Theory of Photographic Process, 4th edition, published by Macmillan, 1977, (T.
H. James, The Theory of the
Photographic Process, 4th
ed, Macmillan, 1977) 67-76 and using active gelatin, or Research Disclosure, 120 vol.
April 1974, 12008; Research Disclosure, Volume 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361 and 3,297,446;
Nos. 3,772,031, 3,857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent No. 1,31
PAg 5-10, pH as described in US Pat.
Sulfur, selenium at 5-8 and a temperature of 30-80 ° C.
It can be carried out using tellurium, gold, platinum, palladium, iridium, rhodium or combinations of these sensitizers. Chemical sensitization is optimally carried out in the presence of gold and thiocyanate compounds and also in US Pat. No. 3,857,71.
Nos. 1, 4,266,018 and 4,054,4
No. 57, or in the presence of a sulfur-containing compound such as a hypo, a thiourea compound, and a rhodanine compound.

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. Compounds known to suppress fog and increase sensitivity in the course of chemical sensitization, such as azaindene, azapyridazine and azapyrimidine, are used as the chemical sensitization aid. Examples of chemical sensitization aids are
U.S. Pat. Nos. 2,131,038 and 3,411,91
4, 3,554,757, JP-A-58-1265.
36 and Daffin, "Photoemulsion Chemistry", 138-14.
See page 3 (published by Focal Press, 1966).

In addition to or in place of chemical sensitization, US Pat. Nos. 3,891,446 and 3,984,24
It can be reduction sensitized with, for example, hydrogen as described in US Pat. No. 2,518,698.
No. 2,743,182 and No. 2,743,18
Reduction sensitization with stannous chloride, thiourea dioxide, polyamines and such reducing agents as described in No. 3 or by low pAg (eg less than 5) or high pH (eg greater than 8) treatment. be able to. U.S. Pat. Nos. 3,917,485 and 3,966,47.
The chemical sensitization method described in No. 6 can also be applied.
Further, a sensitizing method using an oxidizing agent described in JP-A Nos. 61-3134 and 61-3136 can also be applied.

During the production of an emulsion containing tabular grains of the present invention, a silver salt solution (eg, AgNO ₃ aqueous solution) and a halide solution (eg, KB), which are added to accelerate grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the (r aqueous solution) is preferably used. For these methods,
For example, British Patent No. 1,335,925, U.S. Patent Nos. 3,672,900, 3,650,757, 4,242,445, JP-A-55-142329,
The description in No. 55-158124 can be referred to.

A silver halide solvent is useful for promoting the ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Therefore, introduction of the halide salt solution into the reactor can accelerate aging. Other ripening agents can be used, these ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, and one or more ripening agents can be used. And a peptizer may be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

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

The properties of the silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor. In addition, one or more salts can be added together with the salt according to a conventional method. US Patent Nos. 2,448,060 and 2,628,167
Issue 3, Issue 3,737,313, Issue 3,772,031
Issue, and Research Disclosure, Vol. 134,
June 1975, 13452, copper, iridium, lead, bismuth, cadmium, zinc, (sulfur,
Chalcogen compounds such as selenium and tellurium), gold and
The properties of silver halide can be controlled by allowing a compound such as a compound of Group VII noble metal to be present during the silver halide precipitation formation process. Japanese Patent Publication No. 58-1410,
Moisar et al., Journal of Photographic Science, 25, 1977,
As described on pages 19 to 27, the silver halide emulsion can reduce and sensitize the inside of the grain during the precipitation formation process.

In the tabular grains used in the present invention,
Silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and oxides. These emulsion grains are described in US Pat. No. 4,094,68.
No. 4, No. 4,142,900, No. 4,459,353
No., British Patent No. 2,038,792, US Patent No. 4,
349,622, 4,395,478, 4,4
33,501, 4,463,087, 3,65
6,962, 3,852,067, JP-A-59-
No. 162540 and the like.

The emulsion containing tabular grains used in the present invention can be used together with ordinary silver halide grains (hereinafter referred to as "non-tabular grains") in the same silver halide emulsion layer. In the case of materials, the tabular grain-containing emulsion and the non-tabular grain-containing emulsion can be used in different emulsion layers and / or the same emulsion layer. Here, as the non-tabular grains, for example, cubic grains, octahedrons, regular grains having regular crystalline bodies such as tetradecahedrons and spherical grains,
Examples thereof include particles having an irregular crystal shape such as a potato shape. The silver halide composition of these grains includes silver bromide, silver iodobromide, silver iodochlorobromide,
Either silver chlorobromide or silver chloride may be used, but silver bromide or silver chlorobromide is preferred. The non-tabular grains used herein may be fine grains of 0.1 μm or less, large grains having a projected area diameter of up to 10 μm, monodisperse emulsions having a narrow distribution, or polydispersions having a wide distribution. An emulsion may be used.

The non-tabular grains used in the present invention are those described by Graphkid, "Physics and Chemistry of Photography," published by Paul Montel (P. Glafkides, Chimie et Ph.
ysique Photographique, Pau
l Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffi).
n, Photographic Emulsion C
hemistry, Focal Press, 196
6), "Production and Coating of Photographic Emulsion", by Zerikman et al., Published by Focal Press (VL Zelikman et al.).
al, Making and Coating Pho
topographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion comprising the above regular grains can be obtained by controlling pAg and pH during grain formation. For more information, for example,
Science and Engineering (Photog
raphic science and engineering
ering), Vol. 6, 159-165 (196)
2); Journal of Photographic Science (Journal of Photographics)
c Science), Volume 12, pp. 242-251 (1
964), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748. For monodisperse emulsions, JP-A-48-8600 and 51-51
-39027, 51-83097, 53-13.
No. 7133, No. 54-48521, No. 54-9941
No. 9, No. 58-37635, No. 58-49938,
Japanese Patent Publication No. 47-11386, U.S. Pat. No. 3,655,3
94 and British Patent No. 1,413,748.

The crystal structure of these non-tabular grains may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are disclosed in British Patent 1,027,146, U.S. Pat. Nos. 3,505,068, 4,444,877 and JP-A-58-248469. Here, the monodisperse silver halide emulsion (non-tabular grain) means the total weight or the total number of silver halide grains contained in the emulsion.
5% or more is within ± 40% of the average particle size, more preferably ±
Defined to be within 30%.

As described above, the tabular grains and non-tabular grains used in the present invention are usually those which have undergone physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are Research Disclosure N
o. No. 17643 and the same No. 18716.

In the present invention, a more preferable effect can be obtained by allowing a sensitizing dye to be present during chemical sensitization. As the sensitizing dye, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, U.S. Pat. Nos. 3,522,052, 3,619,197, 3,713,828, 3,615,643 and 3,3. 615,632, 3,617,293, 3,628,964, 3,703,377, 3,666,480, 3,667,960, 3,679. No. 428, No. 3,672,897, No. 3,769,026, No. 3,556,800, No. 3,615,613, No. 3,615,638, No. 3,615,635. , 3,705,809, 3,632,349, 3,677,765, 3,770,449, 3,770,440, 3,769,025, No. 3,745,014, No. 3,713,828, No. 3,567,45 No., the 3,625,698 Patent, the 2,526,632 Patent, the 2,503,776 Patent, JP 48-76525, Belgian Patent No. 691,807
No. etc. The addition amount of the sensitizing dye is 0.1 mmol or more, preferably 0.1 mmol or more and 4 mmol or less, and more preferably 0.2 mmol or more and 1.5 millimolar or less, per mol of silver halide.

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

The term "white support" as used in the present invention means a support having a white color on at least the side on which the dye image-receiving layer is coated, and any support having sufficient whiteness and smoothness can be used. Can be done. For example, particle size 0.1 to 5 μm
Of titanium oxide, barium sulphate, zinc oxide and other white pigments are added and stretched to form microvoids, resulting in whitening of polymer films, such as polyethylene terephthalate, polystyrene, and polypropylene films and synthetic films formed by conventional sequential biaxial stretching. It is preferable to use paper, or a paper obtained by laminating polyethylene, polyethylene terephthalate, polypropylene or the like on both sides of the paper. A white pigment such as titanium white may be kneaded in the laminate layer. The thickness of the support is 50-350μ
m, preferably 70 to 210 μm, more preferably 80
１５０150 μm. If necessary, a light-shielding layer may be provided on the support. For example, a support obtained by laminating polyethylene containing a light-shielding agent such as carbon black on the back of a white support is used.

Examples of the black support include polyethylene terephthalate, cellulose acetate, polycarbonate, polystyrene and the like having a thickness of 50 to 350 μm, preferably 70 to 210 μm, containing a light-shielding agent such as carbon black.
A thickness of 50 to 400 μm, preferably 70 including a light shielding agent such as polypropylene or carbon black.
A paper support having a thickness of up to 250 μm laminated with polyethylene, polyethylene terephthalate, polypropylene or the like on both sides is preferably used. As the carbon black raw material, for example, Donnel Voest “Ca
rbon Black "Marcel Dekker
Inc. , (1976), such as a channel method, a thermal method, and a furnace method 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 according to the sensitivity of the light-sensitive material to be shielded, but it is 5 to the optical density.
About 10 is desirable. When a black support is used or when the whiteness of a white support is insufficient, it is necessary to provide a white light reflecting layer between the support and the dye image-receiving layer, and the particle size is 0.1 to 5 μm. Titanium oxide, barium sulfate,
It is preferable to provide a layer containing a white pigment such as zinc oxide or a hollow polymer latex.

(B) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming substance is provided. The components will be described below. (1) Dye image-forming substance The dye image-forming substance used in the present invention (hereinafter, referred to as a reducible dye-donor compound) does not itself release a dye in connection with silver development, but it is a dye when reduced. Is to be released. This type of compound can be used in combination with an electron donor to release an imagewise diffusible dye upon reaction with the remaining electron donor which has been imagewise oxidized by silver development. For the atomic group having such a function, see, for example, US Pat. Nos. 4,183,753 and 4,1.
42,891, 4,278,750, 4,13
9,379, 4,218,368, JP-A-53-
110827, U.S. Pat. Nos. 4,278,750, 4,356,249, 4,358,525, JP-A-53-1108827, 54-130927, 56-164342, and U.S.A. Patent No. 4,783,396
Issue, open technical report 87-6199, European Patent Publication No. 220,
746A2.

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

First, the PWR will be described in detail. P
WR is US Pat. Nos. 4,139,389 and 4,13.
9,379, 4,564,577, JP-A-59-
As disclosed in Japanese Patent No. 185333 and No. 57-84453, a moiety containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound which releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced. Or U.S. Pat. No. 4,232,107, JP-A-59-101649, Research Disclosure (1984) IV, 24025 or JP-A-61-8.
No. 8257, corresponding to the electron-accepting quinonoid center and the portion containing the carbon atom linking it to the photographic reagent in the compound that releases the photographic reagent by an electron transfer reaction in the molecule after reduction. It may be one. Also, JP-A-56-142530, U.S. Pat. Nos. 4,343,893 and 4,619,884.
As disclosed in U.S. Pat. No. 4,962,819, an aryl group substituted with an electron-withdrawing group in a compound that releases a photographic reagent by cleavage of a single bond after reduction and an atom (a sulfur atom, a carbon atom or a nitrogen atom) connecting the aryl group to the photographic reagent. It may correspond to a portion including an atom. U.S. Pat. No. 4,450,2
No. 23, which may correspond to a nitro group in a nitro compound which releases a photographic reagent after electron acceptance and a portion containing a carbon atom which connects the nitro group and the photographic reagent, and is disclosed in US Pat. No. 4,609,610, which corresponds to a geminal dinitro moiety in a dinitro compound that beta-eliminates a photographic reagent after electron acceptance and a part containing a carbon atom connecting the nitro reagent to the photographic reagent. Is also good. Further, a compound having SO ₂ —X (X represents oxygen, sulfur or nitrogen) and an electron-withdrawing group in one molecule described in US Pat. No. 4,840,887,
In one molecule described in JP-A-63-271344, PO
A compound having a -X bond (X is the same as above) and an electron-withdrawing group, a C-X 'bond (X' is synonymous with X or -SO in one molecule described in JP-A-63-271341. _2- represents) and a compound having an electron-withdrawing group.

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

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(Time) _t -Dye is R ¹⁰¹ , R ¹⁰²
Alternatively, it binds to at least one of EAGs. The part corresponding to PWR in the general formula ( I ) will be described. X represents an oxygen atom (—O—), a sulfur atom (—S—), or a group containing a nitrogen atom (—N (R ¹⁰³ ) —). R ¹⁰¹ , R
¹⁰² and R ¹⁰³ represent a group other than a hydrogen atom or a simple bond. Examples of the group other than the hydrogen atom represented by R ¹⁰¹ , R ¹⁰² and R ¹⁰³ include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a sulfonyl group, a carbamoyl group and a sulfamoyl group. May have a substituent. R ¹⁰¹ and R ¹⁰³ are preferably substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups and the like. R ¹⁰¹ and R ¹⁰³
The carbon number of is preferably 1 to 40. R ¹⁰² is preferably a substituted or unsubstituted acyl group or sulfonyl group. The carbon number is preferably 1-40. R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may combine with each other to form a 5- to 8-membered ring. Oxygen is particularly preferable as X. The EAG will be described later.

In order to further achieve the object of the present invention, among the compounds represented by the general formula ( II ), those represented by the general formula ( III) are preferred.

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(Time) _t -Dye is R ¹⁰⁴ , EAG
To at least one of the. X has the same meaning as above. R ¹⁰⁴ is X, attached to the nitrogen atom, represent an atomic group forming a monocyclic or condensed heterocyclic five or eight-membered, including a nitrogen atom.

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

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In the general formula (A), Z ₁ represents a group represented by Chemical formula 4 or> N-.

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V _n represents an atomic group forming a 3- to 8-membered aromatic with Z ₁ and Z ₂ , and n represents an integer of 3 to 8. _{V 3; -Z 3 -, V} 4; -Z 3 -Z 4 -, V 5; -Z 3
_{-Z 4 -Z 5 -, V 6} ; -Z 3 -Z 4 -Z 5 -Z 6 -, V 7; -Z 3 -Z
_{4 -Z 5 -Z 6 -Z 7 -} , V 8; -Z 3 -Z 4 -Z 5 -Z 6 -Z 7 -Z 8 - a. Z _{2 to} Z ₈ each represent a group represented by Chemical formula 5, a group represented by Chemical formula 6, —O—, —S—, or —SO ₂ —,
Sub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. Subs may be the same or different, and may be bonded to each other to form a 3- to 8-membered saturated or unsaturated carbocycle or heterocycle.

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

EAG is preferably an aryl group substituted with at least one electron-withdrawing group, or a heterocyclic group. The substituent bonded to the aryl group or heterocyclic group of EAG can be used for controlling the physical properties of the entire compound. Examples of physical properties of the whole compound include, in addition to being able to adjust the ease of receiving electrons, for example, water solubility, oil solubility, diffusibility, sublimability, melting point, dispersibility in a binder such as gelatin, reactivity to a nucleophilic group, It can be used to adjust the reactive group for an electrophilic group. A specific example of EAG is US Pat.
No. 3,396, European Patent Publication No. 220,746A2, No. 6
~ Page 7.

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

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

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

Examples of magenta dyes: US Pat. Nos. 3,453,107 and 3,544,54.
No. 5, No. 3,932, 380, No. 3,931, 144
No. 3,932,308, No. 3,954,476
Issue No. 4,233,237 Issue 4,255,509
No. 4,250,246, No. 4,142,891
Issue 4,207,104, 4,287,292
JP, JP-A-52-106727, the same 53-23628
Nos. 55-36804, 56-73057, 56-71060 and 55-134.

Examples of cyan dyes: US Pat. No. 3,482,
972, 3,929,760, 4,013,6
No. 35, No. 4,268,625, No. 4,171,2
No. 20, No. 4,242, 435, No. 4, 142, 89
1, No. 4,195,994, No. 4,147,544
No. 4,148,642, British Patent No. 1,551,
138, JP-A-54-99431 and JP-A-52-882.
No. 7, No. 53-47823, No. 53-143323.
54-99431, 56-71061, European Patent (EPC) 53,037, 53,04.
No. 0, Research Disclosure N
o. 17630 (1978) and 16475 (1)
977).

As a kind of dye precursor, a diffusion resistant dye-providing compound having a dye whose absorption spectrum is temporarily shifted can be used during storage and exposure of the light-sensitive material. The dye whose absorption spectrum is temporarily shifted (hereinafter referred to as a temporary shift dye) means a dye whose absorption spectrum is different from the original absorption spectrum when observed as an image. , The diffusion-resistant dye-providing compound may have an original absorption spectrum at the same time as when it is released, or may have an original absorption spectrum at the time of development independently of the emission. The original absorption spectrum may be obtained after reaching. The dyes used here include yellow, magenta, cyan, black, etc., and when these dyes are structurally classified, nitro and nitroso dyes, azo dyes (benzeneazo dyes, naphthalene azo dyes, heterocyclic azo dyes, etc.), stilbene dyes. Dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoline dyes, methine dyes (polymethine dyes, azomethine dyes, etc.), thiazole dyes, quinoneimine dyes (azine dyes, oxazine dyes, thiazine dyes, etc. ), Lactone dyes, aminoketone dyes, hydroxyketone dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, etc., and preferred temporary shift dyes are azo dyes and carbonium dyes. , Anthraquinone dyes, methine dyes and quinone imine dyes, particularly preferred are azo dyes.

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

Regarding these methods, in the method in which the auxochrome is chemically blocked, the release and deblocking of a dye occur independently as described in JP-A-57-158538 and JP-A-57-58638.
Nos. 5,53,329 and 55-53330. Examples of other block methods more generally described are U.S. Pat. No. 4,009,0.
No. 29, 4,310,612, 3,674,47
No. 8, 3,932, 480, 3,993,661
Nos. 4,335,200 and 4,363,865
No. 4,410,618. Further, as an example in which the release and deblocking of the dye occur at the same time, it is described as a specific example in US Pat. No. 4,783,396. Further, a method of changing to a dye having a desired absorption spectrum by chelating with a metal ion after reaching the image receiving layer is disclosed in JP-A-58-209742.
Nos. 58-209741 and 58-17438, 5
8-17437, 58-17436, 57-1
Nos. 85039 and 57-58149; U.S. Pat.
204,993, 4,148,642, 4,1
47,544 and JP-A-57-158637, 58
-123537, 57-181546, 60-
Nos. 57837, 57-182738, 59-20
No. 8551, No. 60-37555, No. 59-1544
No. 8, No. 59-149362, No. 59-164553.
An example is described in the issue.

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

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

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

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

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In the formula, A ¹⁰¹ and A ¹⁰² each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group which can be deprotected by a nucleophile. Here, as the nucleophile,
OH ^-, RO ^- (R; alkyl group, an aryl group),
Examples thereof include anionic reagents such as hydroxamic acid anions and SO ₃ ^2−, and compounds having non-shared electron pairs such as primary or secondary amines, hydrazine, hydroxylamines, alcohols and thiols. In the formula, when A ¹⁰¹ and A ¹⁰² represent a group which can be removed by an alkali (hereinafter referred to as a precursor group), it is preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxazolyl group or a sulfonyl group. Hydrolyzable groups such as groups, precursor groups of the type utilizing the reverse Michael reaction described in US Pat. No. 4,009,029, US Pat. No. 4,310,61
A precursor group of the type which utilizes an anion generated after the ring opening reaction described in No. 2 as an intramolecular nucleophilic group, U.S. Pat. Nos. 3,674,478, 3,932,480 or 3,993. A precursor group which causes anion transfer of an anion described in US Pat. No. 661 through a conjugated system to thereby cause a cleavage reaction, and a cleavage reaction by electron transfer of a reacted anion after ring opening described in US Pat. No. 4,335,200. Precursor base or US Pat. No. 4,36
Precursor groups utilizing an imidomethyl group described in Nos. 3,865 and 4,410,618 can be mentioned. A ¹⁰¹ and A ¹⁰² are R ²⁰¹ , R ²⁰² and R, if possible.
They may combine with ²⁰³ and R ²⁰⁴ to form a ring. Further, A ¹⁰¹ and A ¹⁰² may be the same or different.

R ²⁰¹ , R ²⁰² , R ²⁰³ and R ²⁰⁴ are each a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group or an amide. Group, imide group, carboxyl group, sulfonamide group and the like. These groups may have a substituent, if possible. However, the total carbon number of R ^{201 to} R ²⁰⁴ is 8 or more. Further, in the general formula ( B ), R
²⁰¹ and R ²⁰² and / or R ²⁰³ and R ²⁰⁴ are, in the general formula ( C ), R ²⁰¹ and R ²⁰² , R ²⁰² and R ²⁰³ and / or R ²⁰³ and R ²⁰⁴ are bonded to each other to form a saturated or unsaturated group. You may form a ring. Among the electron donors represented by the general formula ( B ) or ( C ), R ^{201 to} R ²⁰⁴
Of these, at least two are substituents other than hydrogen atoms. Particularly preferred compounds are those in which at least one of R ²⁰¹ and R ²⁰² and at least one of R ²⁰³ and R ²⁰⁴ are a substituent other than a hydrogen atom.

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

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

(3) Intermediate layer In order to suppress stain of a positive image-forming light-sensitive material using such a reducible dye-donating compound, in addition to a diffusion-resistant electron donor as a reducing agent, It is effective to use an electron transfer agent, but the generated electron transfer agent radicals diffuse to other layers having different color sensitivities, cross-oxidize the electron donor there, and further promote fog development, There is a problem that the color reproduction deteriorates due to the decrease in density. In order to solve these problems, an intermediate layer may be provided between the photosensitive layers having different color sensitivities, or a diffusion resistant reducing agent may be contained in the intermediate layer. Specific examples thereof include non-diffusible hydroquinone, sulfonamidophenol, and sulfonamidonaphthol, and more specifically, Japanese Patent Publication Nos. 50-21249, 50-23813, 49-106326, and 49-129535. No. 2,336,327 and 2,360,290.
No. 2, ibid. 2,403,721, ibid. 2,544,640
Issue 2, Issue 2,732,300, Issue 2,782,659
Issue 2, Issue 3,937,086, Issue 3,637,393
No. 3,700,453, British Patent No. 557,75.
No. 0, JP-A-57-24941 and JP-A-58-21249.
No. etc. Further, regarding the dispersion method thereof, JP-A-60-238831 and JP-B-60-1897.
No. 8 is described. The amount used is in the range of 0.05 mmol to 50 mmol per 1 m ² of support and 0.01 mmol to 50 mmol per 1 g of binder in each intermediate layer. The method for adding the diffusion resistant reducing agent to the intermediate layer includes an oil dispersion method, a polymer dispersion method, a fine particle dispersion method and the like, and any method may be used.

As the binder for the intermediate layer of the present invention, gelatin or a gelatin derivative, a cellulose derivative, a polysaccharide such as dextran, a natural substance such as gum arabic, polyvinyl acetal (preferably having an acetalization degree of 20% or less, for example, Polyvinyl butyral), polyacrylamide, polyvinyl pyrrolidone, ethyl cellulose, polyvinyl alcohol (preferably,
Water-soluble polymers such as those having a saponification rate of 75% or more). Moreover, you may use these binders in mixture of 2 or more types as needed.

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

Polymer particles can also be used as the solid particles of the intermediate layer of the present invention. If necessary, these solid particles may be used in combination of two or more kinds. The average particle diameter of the solid particles contained is 0.005 μm to 1.
It is 0 μm, preferably 0.01 μm to 0.5 μm. The content of solid particles in the intermediate layer of the present invention is preferably 5% by weight or more, more preferably 20 to 100% by weight, based on the binder of the intermediate layer.

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

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

Also, JP-B-51-39853, JP-A-51-39853
A dispersion method using a polymer described in JP-A-59943 can also be used. In addition, it can be directly dispersed in an emulsion, or can be dissolved in water or alcohols and then dispersed in gelatin or an emulsion. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method.
(For example, JP-A-59-174830 and JP-A-53-102)
No. 733, No. 63-271339, etc.) When dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used. For example, JP-A-59-1
Surfactants listed on pages (37) to (38) of No. 57636 can be used.

(5) Silver Halide Emulsion As the silver halide emulsion of the present invention, those described above are used.
The coating amount of the photosensitive silver halide of the present invention is 1 mg in terms of silver.
To 10 g / m ² . It is advantageous to use gelatin as a protective colloid used when preparing the emulsion of the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl. Alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Various synthetic hydrophilic polymer substances such as single or copolymers such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. So
c. Sci. Photo. Japan, No. 16, P
30 (1966) may be used, and a hydrolyzate or enzymatic degradation product of gelatin may also be used.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pp. 24-25, and JP-A-59-1684.
No. 42 nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, a mercapto compound and a metal salt thereof described in JP-A-59-111636, an acetylene compound described in JP-A-62-87957, and the like are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, e b polar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257, and JP-A-59-180550.
No. 60-140335, RD17029 (197
8 years), sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. , 615, 641, and JP-A-63-23145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

(6) Construction of Photosensitive Layer For the reproduction of natural colors by the subtractive color method, the dye which provides a dye having 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 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. In this case, the layer of the reducible dye-providing compound is preferably located under the silver halide emulsion layer in terms of sensitivity. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming substance layer. A partition layer described in JP-B-60-15267 is provided to increase the color image density, and JP-A-60-
It is also possible to increase the sensitivity of the photosensitive element by providing a reflective layer described in No. 91354. In a preferred multilayer structure, a combination unit of 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. When the present invention is used as a photographing material, an ultraviolet absorbing layer can be provided on the uppermost layer of the photosensitive layer. The absorption layer contains
Various UV absorbers generally used in this technical field such as a benzotriazole compound, a 4-thiazolidone compound, and a benzophenone compound can be used.

(C) Dye image receiving layer The dye image receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This may be a single layer or 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 used in the present invention is a polymer having a secondary or tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation group thereof, etc., having a molecular weight of 5,000 or more , It is preferably 10,000 or more. For example, US Pat. Nos. 2,548,564 and 2,484,430,
Vinyl pyridine polymers and vinyl pyridinium cation polymers disclosed in US Pat. Nos. 3,148,061 and 3,756,814; US Pat.
Vinylimidazolium cationic polymers disclosed in U.S. Pat. No. 4,386,693; US Pat. No. 3,625,69
No. 4, 3,859,096, 4,128,538
No. 1, UK Patent No. 1,277,453, etc., and a polymer mordant capable of crosslinking with gelatin and the like; US Pat. Nos. 3,958,995 and 2,721,852.
No. 2,798,063, JP-A-54-11522.
No. 8, No. 54-145529, No. 54-126027.
No. 54-155835, No. 56-17352, and the like; aqueous sol-type mordants disclosed in US Pat. No. 3,898,088; US Pat. No. 4,168,976, No. 4,2
Reactive mordants capable of forming a covalent bond with the dyes disclosed in US Pat. No. 01,840; and US Pat. No. 3,70.
9,690, 3,788,855, 3,64
2,482, 3,488,706, 3,55
7,066, 3,271,147, 3,27
No. 1,148, JP-A Nos. 53-30328 and 52-1.
55528, 53-125, and 53-1024.
No. 53-107835, British Patent No. 2,064,
The mordant disclosed in the specification of No. 802 and the like can be mentioned. In addition, mordants described in U.S. Pat. Nos. 2,675,316 and 2,882,156 can also be mentioned.

Of these mordants, those which do not easily move from the mordant layer to other layers are preferable, for example, those which undergo a crosslinking reaction with a matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type. Mordants are preferred. Particularly preferred is a latex dispersion mordant,
Particle size 0.01 to 2 μm, preferably 0.05 to 0.2 μm
m is preferred. The amount of mordant applied depends on the type of mordant, 4
0.5-10 g, depending on the content of the primary cation group, the type and amount of the dye to be mordanted, the type of binder used, etc.
/ 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.

An anti-fading agent may be used in the image receiving layer. As the anti-fading agent, for example, an antioxidant, an ultraviolet absorber,
Or there is some kind of metal complex. These are substantially contained in the image receiving layer, but can be added to other layers if the effect is obtained. Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat.
2,681), benzophenone compounds (JP-A-46-2784, etc.), and other JP-A-54-4853.
5, No. 62-136641, No. 61-88256, and the like. Also, Japanese Patent Laid-Open No. 62-2601
The ultraviolet absorbing polymer described in No. 52 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3 to 36, and 4,254,1.
No. 95, columns 3-8, JP-A Nos. 62-174741, 6
1-88256, pp. 27-29, JP-A-1-7
5568 and JP-A-63-199248. Examples of useful anti-fading agents are disclosed in
2-215272 (125)-(137). An anti-fading agent for preventing fading of the dye transferred to the image-receiving element may be contained in the image-receiving element in advance, or may be supplied to the image-receiving element from outside such as a light-sensitive element or a processing composition. Good. The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other.

A fluorescent whitening agent may be used in the light-sensitive element and the image-receiving element. In particular, if the image receiving element contains a fluorescent whitening agent,
It is preferably incorporated in the light-sensitive element or the processing composition and supplied to the image-receiving element during the processing step. As an example,
K. Venkataraman ed. “The Chem
Examples include compounds described in “istry of Synthetic Dyes”, Volume V, Chapter 8, JP-A-61-143752 and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with an anti-fading agent.

(D) Layer Having Neutralizing Function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize an alkali carried from the treatment composition, and is required. Depending on the situation, a multi-layered structure including layers such as a neutralization rate adjusting layer (timing layer) and an adhesion enhancing layer may be used. The preferred acidic substance is a substance containing an acidic group having a pKa of 9 or less (or a precursor group which gives such an acidic group by hydrolysis), and more preferably olein described in US Pat. No. 2,983,606. Higher fatty acids such as acids, US Pat. No. 3,362,8
Polymers of acrylic acid, methacrylic acid or maleic acid and partial esters or acid anhydrides thereof as disclosed in No. 19; acrylic acid as disclosed in French Patent No. 2,290,699 Acrylic ester copolymers; US Pat. No. 4,139,383 and Research
Disclosure (Research Disclo
Sure) No. 16102 (1977). In addition, U.S. Pat. No. 4,088,493, JP-A Nos. 52-153739, 53-1023 and 5
No. 3-4540, No. 53-4541, No. 53-454.
The acidic substances disclosed in No. 2 and the like can also be mentioned. Specific examples of the acidic polymer include ethylene, vinyl acetate, vinyl monomers such as vinyl methyl ether, and a copolymer of maleic anhydride and its n-butyl ester, a copolymer of butyl acrylate and acrylic acid, cellulose acetate, Examples include hydrogen diphthalate.

The above-mentioned polymer acid may be used alone or in combination with a hydrophilic polymer. Such polymers include polyacrylamide, polyvinylpyrrolidone,
Polyvinyl alcohol (including partially saponified), carboxymethylcellulose, hydroxymethylcellulose,
Hydroxyethyl cellulose, polymethyl vinyl ether and the like. Among them, polyvinyl alcohol is preferred. Further, a polymer other than the hydrophilic polymer, such as cellulose acetate, may be mixed with the polymer acid. The amount of the polymer acid applied is controlled by the amount of alkali developed on the photosensitive element. The equivalent ratio of the polymer acid to the alkali per unit area is preferably from 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stain is generated on a white background portion. If the amount is too large, inconveniences such as a change in hue and a decrease in light resistance are caused. A more preferred equivalent ratio is 1.0 to 1.3. When mixed with a hydrophilic polymer, the amount of the hydrophilic polymer is too large or too small, and the quality of the photograph is deteriorated. The weight ratio of hydrophilic polymer to polymer acid is 0.1 to 10,
It is 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, hardeners well known to those skilled in the art can be added to harden this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. can be added to improve the brittleness of the film. Other, if necessary,
An antioxidant, a development inhibitor and a precursor thereof can also be added.

(E) Neutralization Timing Layer The timing layer used in combination with the neutralization layer is, for example, gelatin, polyvinyl alcohol, a partial acetalization product of polyvinyl alcohol, cellulose acetate, or partially hydrolyzed polyvinyl acetate. Such polymers that lower alkali permeability; latex polymers that are made by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid monomers to increase activation energy for alkali permeation; polymers that have a lactone ring are useful. . Among them, JP-A-54-136328 and U.S. Pat. No. 4,26.
No. 7,262, No. 4,009,030, No. 4,02
Timing layers using cellulose acetate as disclosed in JP-A No. 9,849; JP-A-54-128335;
6-69629, 57-6843, U.S. Pat. Nos. 4,056,394, 4,061,496, 4,199,362, 4,250,243, 4,256. Latex polymers disclosed in U.S. Pat. No. 4,229,516 disclosed in U.S. Pat. No. 4,229,516, which are disclosed in U.S. Pat. Polymers having a ring; Others, JP-A-56-25735, 5
6-97346, 57-6842, European Patent (EP) No. 31,957A1, 37,724A1.
Nos. 48,412A1 and the like are particularly useful.

In addition, the materials described in the following documents can also be used. U.S. Pat. Nos. 3,412,893 and 3,45
5,686, 3,575,701 and 3,77
8,265, 3,785,815, 3,84
7,615, 4,088,493, 4,12
3,275, 4,148,653, 4,20
1,587, 4,288,523, 4,29
No. 7,431, West German patent application (OLS) 1,622,9
No. 36, No. 2, 162, 277, Research
Disclosure 15162 No. 151 (1
976). JP-A-59-202463, U.S. Pat. No. 4,297,431, US Pat. 56-166212, 55-41490, 55-54341, 56-.
No. 102852, No. 57-141644, No. 57-1.
No. 73834, No. 57-179841, West German Patent Application Publication (OLS) 2,910,271, European Patent Application Publication No. 31,957A1, Research Disc.
loss No. 18452 etc. can be mentioned.

The neutralization timing layer may be a single layer or multiple layers. In the timing layer made of these materials,
For example, U.S. Pat. No. 4,009,029, West German Patent Application (OLS) 2,913,164, and 3,014,67.
No. 2, JP-A Nos. 54-155837 and 55-1387
No. 45, and the like, and a development inhibitor and / or a precursor thereof disclosed in U.S. Pat.
Hydroquinone precursor disclosed in No. 78,
Other useful photographic additives or precursors thereof can be incorporated.

(F) Peeling Layer In the invention, a peeling layer is provided for peeling off the light-sensitive element and the image-receiving element after the treatment, if necessary. Therefore, this release layer must be easily peelable after the treatment. As a material for this, for example, JP-A-47-8237
No. 59-220727 and 59-229555.
No. 49-4653, U.S. Pat. No. 3,220,83.
5, 4,359,518, JP-A-49-4334.
Nos. 56-65133, 45-24075, and U.S. Pat. Nos. 3,227,550 and 2,759,825.
Nos. 4,401,746, 4,366,227 and the like can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. For example, hydroxyethyl cellulose, cellulose acetate-phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. Other examples include various natural polymers, such as alginic acid, pectin, 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,
It is polyacrylate, polymethylmethacrylate, polybutylmethacrylate, or a copolymer thereof. The release layer may be a single layer or may be composed of a plurality of layers as described in JP-A-59-220727 and JP-A-60-60642.

(G) Binder A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive element and the image-receiving element. As an example thereof, Japanese Patent Laid-Open No. 62-62
Examples thereof include those described on pages (26) to (28) of No. 253159. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Also, JP-A-62-245
Superabsorbent polymer described in No. 260, etc., that is, -CO
OM or -SO ₃ M (M is a hydrogen atom or an alkali metal) copolymer of homopolymer or a vinyl monomer together or with other vinyl monomers of the vinyl monomer having a (e.g. sodium methacrylate, ammonium methacrylate, Sumitomo Chemical (Sumikagel L-5H manufactured by Co., Ltd.)
Is also used. These binders can be used in combination of two or more kinds. In the present invention, the coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 1
It is suitable that the amount is 0 g or less, and further 7 g or less.

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

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

[0114]

Embedded image

(I) Others Various surfactants can be used in the constituent layers of the light-sensitive element and the image-receiving element for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. . Specific examples of the surfactant are disclosed in JP-A-62-173463 and JP-A-62-1834.
No. 57 etc. The constituent layers of the photosensitive element and the image receiving element may contain an organic fluoro compound for the purpose of improving sliding property, preventing static charge, improving releasability, and the like. Representative examples of the organic fluoro compound include JP-B-57-9053, No. 8
Column 17, JP-A-61-20944, 62-135
No. 826 or the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin.

A matting agent can be used for the photosensitive element and the image receiving element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
No. 88256 (29), benzoguanamine resin beads, polycarbonate resin beads, A
JP-A Nos. 63-274944 and 6
There is a compound described in 3-274952. In addition, the constituent layers of the photosensitive element and the image receiving element may contain an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A No. 61-88256 (26).
(32).

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the image-receiving element. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), surfactants, silver or silver ions. And compounds that interact with However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. For details of these, see US Pat. No. 4,6.
No. 78,739, columns 38-40.

(J) Processing Composition The processing composition used in the present invention is one which is uniformly spread on the photosensitive element after exposure of the photosensitive element, and the photosensitive layer is developed by the components contained therein. For this purpose, the composition contains an alkali, a thickening agent, a light-blocking agent, an electron transfer agent (developer), and further, a development accelerator for controlling development, a development inhibitor, and a deterioration of the developer. Contains an antioxidant. If necessary, the composition may contain a light-shielding agent. The alkali is sufficient to adjust the pH of the solution to 12 to 14, and includes alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide) and alkali metal phosphates (eg, potassium phosphate). , Guanidines, and hydroxides of quaternary amines (eg, tetramethylammonium hydroxide). Of these, potassium hydroxide and sodium hydroxide are preferable.

The thickener is used in order to uniformly spread the treatment liquid.
It is also necessary to maintain close contact between the light-sensitive element and the image-receiving element during development and to prevent the processing liquid component from remaining on the surface of the image-receiving element during peeling. For example, alkali metal salts of polyvinyl alcohol, hydroxyethyl cellulose, and carboxymethyl cellulose are used, and preferably, hydroxyethyl cellulose and sodium carboxymethyl cellulose are used.

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

As the preferable electron transfer agent, any electron transfer agent can be used as long as it cross-oxidizes the electron donor and does not substantially produce stain even when oxidized. Such electron transfer agents may be used alone or in combination of two or more, and may be used in the form of a precursor. Specific examples of these electron transfer agents include aminophenols and pyrazolidinones. Of these, pyrazolidinones are particularly preferable because they produce less stain. For example, 1-phenyl-3-pyrazolidinone, 1-
p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3'-methyl-phenyl) -4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone and the like can be mentioned. The above treatment composition is described in US Pat. No. 2,543,18.
1, No. 2,643,886, No. 2,653,732
Issue No. 2,723,051 Issue 3,056,491
No. 3,056,492, No. 3,152,515, etc., and it is preferable to use by filling a rupturable container by pressure.

(K) Structure of Light-Sensitive Material A color diffusion transfer instant light-sensitive material can be formed by combining the above elements. The color diffusion transfer instant film unit is roughly classified into a peeling type and a peeling-free type, and in the peeling type, a photosensitive layer and a dye image receiving layer are coated on different supports, and after the image exposure, a photosensitive element is formed. A dye image transferred to the dye image-receiving layer is obtained by superposing the dye-image-receiving element, developing the processing composition therebetween, and then peeling off the dye-image receiving element. On the other hand, in the peel-free type, the dye image-receiving layer and the photosensitive layer are coated between the transparent support and the other support, but the image-receiving layer and the photosensitive layer are coated on the same transparent support. There is a form that is coated on another support. In the former case, a white reflective layer is coated between the image receiving layer and the photosensitive layer, and in the latter case, a white pigment is applied to the processing composition developed between the image receiving layer and the silver halide emulsion layer. By containing the dye, the dye image transferred to the image receiving layer can be observed with reflected light.

In the peeling type, the image-receiving element and the light-sensitive element are generally attached to different supports, and in addition to the dye-image-receiving layer as an image-receiving material, a layer having a neutralizing function, a neutralizing timing layer and a peeling layer as required. Is provided. As the support of the image receiving material,
It is preferable to use a white support having a light shielding function. On the other hand, the light-sensitive material is provided with a layer having a neutralization function and a neutralization timing layer, if necessary, in addition to the light-sensitive layer. It is preferable to use a black support having a light-shielding function as the support for the photosensitive material. Regarding the film unit, JP-A-61
The thing described in No. 47956 can be applied. Further, as a peeling type, JP-A-1-198747,
As described in Japanese Patent Application No. 1-68749, a film unit in which a dye image receiving layer / a release layer / a photosensitive layer are attached to the same support in this order can be applied.

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

[0125]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. <Example-1> First, a method for preparing a silver halide emulsion will be described. Preparation of emulsion-A (tabular silver bromide host grains): 0.08
To 1 liter of a 0.8 wt% gelatin aqueous solution containing M potassium bromide, 150 cc of a 2.00 M silver nitrate aqueous solution and a 2.00 M potassium bromide aqueous solution were added by a double jet method while stirring it. To do. During this time, the gelatin aqueous solution was kept at 30 ° C. After the addition, the temperature was raised to 75 ° C. After the addition, 30 g of gelatin was added. After the addition of the first step, 90 cc of 1.0 M silver nitrate aqueous solution was added. Furthermore, after the addition, aging was carried out for 30 minutes. The particles thus formed (hereinafter referred to as seed crystals) were washed by a conventional flocculation method and adjusted to have a pH of 5.0 and a pAg of 7.5 at 40 ° C.
Tenths of the above seed crystals are dissolved in 1 liter of an aqueous solution containing 3% by weight of gelatin, and the temperature is 75 ° C. and pBr is 2.85.
Was kept. After that, 150 g of silver nitrate was added in 60 minutes at an accelerated flow rate (the flow rate at the end was 19 times the flow rate at the start). During this period, pBr was kept at 2.85. Thereafter, the emulsion was cooled to 35 ° C., washed by a conventional flocculation method, and at 40 ° C., pH 6.5, pAg 8.6.
After adjusting to, it was stored in a cool and dark place. 80% of the tabular grains are occupied by hexagonal tabular grains, and the coefficient of variation is 18%. Further, this particle has an average projected area circle equivalent diameter of 1.3 μm and an average thickness of 0.25 μm.
m.

Preparation of emulsion-B (tabular grain having transition on main surface): 500 g of emulsion-A (9 in terms of AgNO ₃ )
(Including 0 g), add 1300 ml of water at 40 ° C +
At a potential of 190 mV (vs. saturated calomel electrode).
160 ml of 34M silver nitrate aqueous solution and 0.8M Na
160 ml of Cl aqueous solution was added in 8 minutes. Here, a lot of fine silver chloride epitaxy was formed on the main surface of the tabular host grains (not at the edges of the tabular grains). After heating to 75 ° C. and physically aging for 12 minutes, 30 ml of 2.5 M aqueous KBr solution was added, and then 160 ml of 0.34 M silver nitrate aqueous solution and 0.34 M KBr aqueous solution were added at 75 ° C. for 8 minutes. Added in. Thereafter, the emulsion was cooled to 35 ° C., washed by a conventional flocculation method, and 50 g of bone gelatin was added.
After adjusting to pH 6.5 and pAg 8.5 at ℃, it was stored in a cool dark place.

Preparation of Emulsion-C (tabular grains free of dislocations): 0.2 at a potential of +190 mV at 40 ° C.
160 ml of 34M silver nitrate aqueous solution and 0.8M KBr
The same procedure as for Emulsion-B was carried out except that the aqueous solution was added for 8 minutes.

Preparation of Emulsion-D (tabular grains having transition only in the edge portion): 500 g of Emulsion-A was mixed with 130 parts of water.
0 ml and 30 ml of 2.5 M KBr aqueous solution were added to 40
At 0 ° C., 100 ml of 0.09 M silver nitrate aqueous solution and 100 ml of 0.09 M KI aqueous solution were added by a double jet for 10 minutes. After heating to 75 ° C. and physically ripening for 12 minutes, 160 ml of 0.34 M silver nitrate aqueous solution and 160 ml of 0.34 M KBr aqueous solution were added in 8 minutes. Thereafter, the same procedure as in Emulsion-B was performed.

Observation of dislocations introduced in tabular grains: emulsion-
The dislocations of B, C and D were directly observed using a transmission electron microscope. The electron microscope is JEM manufactured by JEOL Ltd.
2000FXII, acceleration voltage 200KV, temperature -1
It was observed at 20 ° C. It was found from the transmission photograph that in the emulsion-B, dislocations were present on the entire main surface, while in the emulsion-C, the dislocations were concentrated only on the edge portions of the tabular grains.
In Emulsion-D, no dislocation was found.

Preparation of emulsion-E (silver bromide cubic grains): First, solutions I to III shown in Table 1 were prepared and used to prepare emulsion-E.

[0131]

[Table 1]

For solution I, as shown in Table-2, while maintaining pAg at 7.1 in the first step and the second step, II
Solution and Solution III were added by the double jet method.
After the addition was completed, the emulsion was cooled to 35 ° C., washed by a conventional flocculation method, and 50 g of bone gelatin was added.
After adjusting to pH 6.5 and pAg 8.5 at 0 ° C.,
Stored in a cool dark place.

[0133]

[Table 2]

Preparation of Emulsions for Red Photosensitive Layer-B1, C1, D1 and E1: The following sensitizing dye S-1 was prepared by heating the emulsions of B to E at a temperature of 60 ° C.
And S-2 were added, and 10 minutes later, ammonium thiocyanate was added at 4 × 10 ⁻³ mol per mol of silver, and Na ₂
SO ₃ and KAuCl ₄ were added for chemical ripening, and when the maximum sensitivity was reached, the temperature was lowered to end the chemical sensitization,
Emulsions-B1, C1, D1, E1 were prepared. Sensitizing dye S
-1 and S-2, Na ₂ SO ₃ and KAuCl ₄ were added such that the maximum sensitivity was obtained for each emulsion. Preparation of Emulsion for Green Photosensitive Layer-Preparation of B2, C2, D2 and E2: Emulsion for Red Photosensitive Layer-Except that the sensitizing dye is changed to S-3.
Emulsion-B2, C2, D2 and E2 for green photosensitive layer were prepared in the same manner as in the preparation of B1, C1, D1 and E1. Preparation of Emulsion for Blue Photosensitive Layer-Preparation of B3, C3, D3 and E3: Emulsion for Red Photosensitive Layer-Except that the sensitizing dye is changed to S-4.
B1, C1, D1, E1 Preparation and similarly blue sensitive layer emulsion -B3, C3, and D3, E3 were prepared.

[0135]

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[0136]

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[0137]

[Table 3]

Next, a method for preparing a gelatin dispersion of the dye-donor compound will be described. Yellow dye-donor compound (1) ^*
18 g and 12 g of the high boiling point organic solvent (1) ^* were weighed, 51 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-processed gelatin, 60 cc of water and 1.5 g of sodium dodecylbenzenesulfonate were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a yellow dye-donor compound dispersion.
Dispersions of magenta and cyan dye-donor compounds were made using magenta dye-donor compound (2) ^* or cyan dye-donor compound (3) ^* as well as yellow dye-donor compound.

Next, a method for preparing a gelatin dispersion of an electron donor will be described. 20.6 g of the electron donor (1) ^* and 13.1 g of the high boiling point organic solvent (1) ^* were weighed, and ethyl acetate 12
0 ml was added and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution and 100% 10% aqueous solution of lime-processed gelatin
g, 60 cc of water and 1.5 g of sodium dodecylbenzenesulfonate were mixed by stirring, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a dispersion of electron donors.

Next, a method for preparing a gelatin dispersion of the diffusion resistant reducing agent for the intermediate layer will be described. Diffusion resistant reducing agent (1) ^*
23.5 g and the high boiling point organic solvent (1) ^* 8.5 g were dissolved in 120 ml of ethyl acetate at about 60 ° C. to obtain a uniform solution.
This solution and 100 g of a 10% aqueous solution of lime-processed gelatin,
After stirring and mixing 15 ml of a 5% aqueous solution of surfactant (3) ^* and 0.2 g of sodium dodecylbenzenesulfonate with stirring, the mixture was homogenized for 10 minutes at 10,000 rpm.
Was dispersed. This dispersion is referred to as a dispersion of the diffusion-resistant reducing agent for the intermediate layer. From these, Comparative Photosensitive Element 101 having the constitution shown in Table 4 below was prepared.

[0141]

[Table 4]

[0142]

[Table 5]

[0143]

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[0145]

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[0146]

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The image receiving element was prepared as follows. Paper support: A paper having a thickness of 150 μm laminated with polyethylene on both sides by 30 μm. To the polyethylene on the image receiving layer side, 10% by weight of titanium oxide based on polyethylene is dispersed and added. Back side: (a) 4.0 g / m ^{2 of} carbon black, gelatin 2.
0 g / m ² light-shielding layer. (B) Titanium oxide 8.0 g / m ² , gelatin 1.0 g / m
white layer of m ^2. (C) A protective layer of 0.6 g / m ² of gelatin. They are applied in the order of (a) to (c) and are hardened with a hardener. Image-receiving layer side: (1) A neutralization layer containing 22 g / m ^{2 of} an acrylic acid-butyl acrylate (molar ratio 8: 2) copolymer having an average molecular weight of 50,000. (2) Cellulose acetate having an acetylation degree of 51.3% (the weight of acetic acid released by hydrolysis is 0.513 g per 1 g of the sample), and styrene-maleic anhydride having an average molecular weight of about 10,000 (molar ratio). 1: 1) A second timing layer containing the copolymer at a weight ratio of 95: 5 of 4.5 g / m ² . (3) An intermediate layer containing 0.4 g / m ^{2 of} poly-2-hydroxyethyl methacrylate. (4) Styrene / butyl acrylate / acrylic acid / N
-Methylol acrylamide in a weight ratio of 49.7 / 42.
The polymer latex emulsion-polymerized by 3/4/4 and the polymer latex emulsion-polymerized by methylmethacrylate / acrylic acid / N-methylolacrylamide at a weight ratio of 933/4 are made to have a solid content ratio of 6: 4. A first timing layer that is blended and contains 1.6 g / m ^{2 of} total solids. (5) 3.0 g of a polymer mordant having a repeating unit of the following chemical formula 30, using the compound of the following chemical formula 29 as a coating aid.
An image receiving layer coated with m ² and 3.0 g / m ² of gelatin.

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

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

Then, the emulsions of the second, fifth and eighth layers were changed to emulsions B1 to B3, C1 to C3 and D1 to D3 shown in Table 5 to prepare samples 102 to 107.

[0153]

[Table 6]

After exposing the light-sensitive elements 101 to 107 from the emulsion layer side through a gray color separation filter,
The image-receiving layer side of the image-receiving element was superposed and the treatment liquid was spread between both materials so as to have a thickness of 60 μm with the aid of a pressure roller. The processing was carried out at 25 ° C., and after 1.5 minutes, the light-sensitive material and the image-receiving element were peeled off. The reflection density transferred to each image receiving element was measured with a color densitometer. The results are shown in Table-6.

[0155]

[Table 7]

[0156]

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

Claims (2)

(57) [Claims] 1. A support having at least one photosensitive silver halide emulsion layer in combination with a dye image-forming substance and an electron donor, wherein the dye image-forming substance is represented by the following general formula (I). The total projected area of silver halide emulsion grains comprising at least one reducible dye-donating compound which releases a diffusible dye when reduced and is contained in at least one emulsion layer of the silver halide emulsion layer. At least 50% of which are occupied by tabular silver halide grains having an average grain diameter of 0.3 μm or more, an average grain thickness of less than 0.5 μm, and an average grain diameter / average grain thickness ratio of 2 or more. And a parallel main surface with which the tabular grains face each other is composed of (111) faces, and at least 30% of the tabular grains have dislocations on the main surface. Transferring the photosensitive material. General formula (I) PWR- (Time) _t -Dye In the formula, PWR is reduced to give-(Tim).
e) represents a group that releases _t- Dye. Time is PWR
Represents a group that is released as-(Time) _t -Dye and then releases Dye through a subsequent reaction. t is 0
Or represents an integer of 1. Dye represents a dye or its precursor. 2. The color diffusion transfer light-sensitive material according to claim 1, wherein at least 50% of the total projected area of silver halide emulsion grains contained in at least one of the silver halide emulsion layers is an average grain. A color diffusion transfer photosensitive material having a diameter of 0.3 μm or more, an average particle thickness of less than 0.5 μm, and an average particle diameter / average particle thickness ratio of 5 or more.