JPH07333771A - Direct positive silver halide emulsion and color photographic material using same - Google Patents

Abstract

PURPOSE:To provide an internal latent image type direct positive silver halide emulsion which has high sensitivity and low re-reversal negative sensitivity and to provide a color diffusion transfer photographic material using the same. CONSTITUTION:In an internal latent image type direct positive silver halide emulsion which is characterized in that flake silver halide particles with an average particle diameter of 0.3mum or more and an aspect ratio (the diameter of silver halide particle equivalent to a circle/particle thickness) of 2 to 100 inclusive are contained therein by 50 % or more of all silver halide particles, the average particle thickness (a) of an outer shell in the direction of the principal plane is 0.2 to 1.5mum inclusive and the average particle thickness (b) of the outer shell in a direction perpendicular to the principal plane is 0.04 to 0.30mum inclusive.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an internal latent image type direct positive silver halide emulsion and a color diffusion transfer light-sensitive material using the same.

[0002]

2. Description of the Related Art The photographic method using a silver halide emulsion is superior to other photographic methods such as electrophotography and diazo photography.
It has excellent sensitivity and gradation characteristics, and has been widely used in the past. Among them, a method of directly forming a positive image is known. This is, for example, US Pat. No. 3,761,
No. 276 and Japanese Patent Publication No. 60-55821, an internal latent image type direct positive silver halide emulsion is developed by a surface developing solution (a latent image forming site inside a silver halide grain is substantially left undeveloped. When developing with a liquid, a positive image is obtained by giving uniform exposure or by using a nucleating agent. Such a direct positive silver halide emulsion is superior to the negative type emulsion in that a positive image can be obtained by a single processing. Generally, an internal latent image type direct positive silver halide emulsion is prepared by mixing a soluble silver salt and a soluble halide in a gelatin aqueous solution to form silver halide grains (hereinafter referred to as
Core grains), and after this, chemical sensitization of the core grains is performed, followed by silver halide deposition for shell formation, followed by desalting and, if necessary, chemical sensitization. Is prepared. For example, Japanese Patent Publication Sho 52-3
No. 4,213 (US Pat. No. 3,761,276) describes an internal latent image type emulsion useful as a direct positive emulsion, which emulsion contains a dopant inside a silver halide grain, and has a grain surface. It is characterized by chemical sensitization. This is also shown in US Pat. No. 3,317,322 to Porter et al.

On the other hand, the present invention relates to tabular silver halide grains, but the tabular silver halide grains have already been described by Cleve in "The Theory and Practice of Photography" (Cleve, Ph.
otography Theory and Practice 1930)), 131
Page: Gutoff, Photographic Science and Engineering
and Engineering), Volume 14, pp. 248-257 (1
970); U.S. Pat. Nos. 4,434,226, 4,
No. 414, 310, No. 4,433, 048, No. 4, 4
39,520, 4,414,306, 4,45
No. 9,353, British Patent No. 2,112,157, JP-A-59-99433, JP-A-62-209445, and the like, their manufacturing methods and use techniques are disclosed. Particularly, tabular internal latent image type direct positive silver halide emulsions are disclosed in US Pat. Nos. 4,395,478 and 4,504,570.
No. 4,996,137, Japanese Patent Publication No. 64-8327.
JP-A-1-131547 and JP-A-1-154414.
No. 2, JP-A No. 1-158429, and JP-A No. 1-2976.
No. 49, etc. These tabular internal latent image type direct positive emulsions are excellent in that they have a good sharpness, a rapid development progress, and a direct positive image having a small development temperature dependency.

However, the tabular internal latent image type direct positive silver halide emulsion prepared in this manner has a drawback that a reversal negative image, which is often seen, is likely to be formed upon exposure to high illuminance. To solve this problem,
As a means for reducing the re-inversion negative image, a method of doping polyvalent metal ions into silver halide grains is disclosed in U.S. Pat. Nos. 3,367,778, 3,287,136 and 4,395,478. However, even if this method is applied to a tabular internal latent image type direct positive silver halide emulsion, a sufficient improvement effect cannot be obtained. Therefore, there has been a demand for the development of a tabular internal latent image type direct positive silver halide emulsion in which the excellent characteristics of the tabular internal latent image type direct positive silver halide emulsion are not impaired and a re-inversion negative image is hard to occur. .

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a tabular internal latent image type direct positive silver halide emulsion having high sensitivity and low re-reversal negative sensitivity, and a color diffusion transfer light-sensitive material using the same. Is to provide.

[0006]

The object of the present invention has been achieved by the following internal latent image type direct positive silver halide emulsions and color diffusion transfer light-sensitive materials using the same. (1) Average grain diameter of 0.3 μm or more, aspect ratio (diameter of silver halide grain equivalent to circle / grain thickness) of 2 or more 10
In an internal latent image type direct positive silver halide emulsion characterized by containing tabular silver halide grains of 0 or less in an amount of 50% or more of all silver halide grains, the average grain thickness a of the outer shell in the main plane direction is The internal latent image type direct positive halogen is 0.2 μm or more and 1.5 μm or less, and the average grain thickness b in the direction perpendicular to the main plane of the outer shell is 0.04 μm or more and 0.30 μm or less. Silver halide emulsion. (2) In the internal latent image type direct positive silver halide emulsion described in (1) above, the average grain thickness a of the outer shell in the main plane direction is a.
Is 0.4 μm or more and 1.0 μm or less, and the average particle thickness b in the direction perpendicular to the main plane of the outer shell is 0.06 μm.
An internal latent image type direct positive silver halide emulsion characterized by having a size of m or more and 0.15 μm or less. (3) In the internal latent image type direct positive silver halide emulsion as described in the above item (1) 1, the internal latent image type direct positive halogenation is characterized in that the coefficient of variation of grain thickness is 30% or more and the uniformity is high. Silver emulsion. (4) In the internal latent image type direct positive silver halide emulsion described in (1) above, in the presence of at least one compound selected from the compounds represented by the following general formulas [A], [B] and [C]. An internal latent image type direct positive silver halide emulsion characterized in that a silver halide phase is formed in the outer shell.

[0007]

[Chemical 2]

In the formula, R, R _{1 and} R ₂ may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compound represented by the general formula [A], [B], or [C] is a polymer containing a divalent group derived from the structure represented by [A], [B], or [C] as a repeating unit. May be. If possible, R, R ₁ , R ₂ and L may be connected to each other to form a ring. (5) A silver halide color light-sensitive material comprising at least one internal latent image type direct positive silver halide emulsion described in (3) and (4). (6) Relating to silver development, having on a support at least one light-sensitive silver halide emulsion layer combined with a dye image-forming substance, which dye-image forming substance is represented by the following general formula [I]: In a color diffusion transfer light-sensitive material comprising a non-diffusible compound which releases a diffusible dye or a precursor thereof, or a compound whose diffusivity of itself changes, at least one layer of the silver halide emulsion comprises ), (2),
Alternatively, a color diffusion transfer photosensitive material containing at least one internal latent image type direct positive silver halide emulsion described in (3). General formula [I] (DYE-Y) n-Z {DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like structure. To produce a difference in the diffusivity of the compound represented by (DYE-Y) n-Z corresponding to or opposite to the photosensitive silver salt having a latent image, or to release DYE and release DYE and ( DYE-Y) n -Z represents a group having a property of causing a difference in diffusibility,
n represents 1 or 2, and when n is 2, two DYE-Y may be the same or different. }

The specific structure of the present invention will be described in detail below. The present invention is applied to internal latent image type direct positive silver halide emulsions. An internal latent image type direct positive silver halide emulsion (hereinafter sometimes abbreviated as an internal latent image type silver halide emulsion) means that a latent image is mainly formed inside a silver halide grain when imagewise exposed. A silver halide emulsion, specifically, a silver halide emulsion is coated on a transparent support in a fixed amount, and exposed to light for a fixed time of 0.01 to 1 second. 2 in "internal" developer)
The maximum density obtained when developed at 0 ° C. for 5 minutes is the same as when the second sample exposed as described above was developed at 20 ° C. for 5 minutes in the following developer B (“surface type” developer). Defined as having a concentration at least 5 times greater than the maximum concentration obtained. Here, the maximum density is measured by a usual photographic density measuring method. Developer A N-methyl-p-aminophenol sulfite 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Sodium carbonate (monohydrate) 52.5g Potassium bromide 5g Potassium iodide 0.5g Water added 1 liter Developer B N-methyl-p-aminophenol sulfite 2.5 g 1-ascorbic acid 10 g potassium metanitrate 35 g potassium bromide 1 g Water added 1 liter As an internal latent image type silver halide emulsion, for example, US Pat. , 953 and 2,592,250, etc., and conversion type silver halide emulsions, and the first and second phases as described in US Pat. No. 3,935,014. Laminated structure type silver halide emulsion with different halogen composition, or dope metal ion,
Alternatively, a core / shell type silver halide emulsion obtained by coating a chemically sensitized core grain with a shell may be used. Of these, a core / shell type silver halide emulsion is particularly preferable as the internal latent image type silver halide emulsion used in the present invention, and examples thereof include U.S. Pat. Nos. 3,206,313 and 3,31.
7,322, 3,761,266, 3,76
1,276, 3,850,637, 3,92
No. 3,513, No. 4,035,185, No. 4,18
No. 4,878, No. 4,395,478, No. 4,504,
570, JP-A-57-136641 and 61-31.
37, JP-A-61-299155, JP-A-62-208
241 etc. are mentioned. In order to directly obtain a positive image, a uniform second exposure is applied to the front surface of the exposed layer after the above-mentioned internal latent image type silver halide emulsion is imagewise exposed and before or during the development treatment (the "light fog method"). Development process in the presence of a nucleating agent ("chemical fogging", e.g. Research Disclosur, U.S. Pat. No. 1,151,363).
e), Volume 151, No. 15162, pp. 76-78), the method of directly obtaining a positive image by the "chemical fogging method" is preferred in the present invention. The nucleating agent used in the present invention will be described later. As described above, in order to directly obtain a positive image using the internal latent image type silver halide emulsion, after the image exposure, before the development processing or during the development processing, the entire surface is uniformly exposed to the second exposure, or It is obtained by carrying out development processing in the presence of a nucleating agent. Examples of the nucleating agent include U.S. Patents 2,563,785 and 2,588,
Hydrazines described in 982, US Pat.
Hydrazides, hydrazones described in 7,552,
British Patent 1,283,835, JP-A-52-6961
3, No. 55-138742, No. 60-11837,
62-210451, 62-291637, U.S. Patents 3,615,515, 3,719,494, 3,734,738, 4,094,683, and 4,1.
15, 122, 4306016, 4471044 and the like, heterocyclic quaternary salt compounds, US Pat.
Sensitizing dyes having a nucleating substituent in the dye molecule, described in US Pat. No. 4,030,92.
5, the same 4,031,127, the same 4,245,037, the same 4,255,511, the same 4,266,013, the same 4,2
76,364, thiourea-bonded acylhydrazine compounds described in British Patent 2,012,443, etc., and US Pat. The thiohydrazine ring or the sialhydrazine compound having a heterocyclic group such as triazole or tetrazole bonded as an adsorption group is used. The amount of the nucleating agent used here is preferably an amount that gives a sufficient maximum density when the internal latent image type emulsion is developed with a surface developing solution. Practically, since the content of the silver halide emulsion to be used, the chemical structure of the nucleating agent and the development conditions vary, the appropriate content may vary over a wide range. A range of about 0.1 mg to 5 g per mole is practically useful,
It is preferably about 0.5 mg to 2 g per mol of silver. When contained in the hydrophilic colloid layer adjacent to the emulsion layer,
The same amount as described above may be added to the amount of silver contained in the inner latent type emulsion having the same area.

The present invention is applied to a tabular internal latent image type direct positive silver halide emulsion. The outer shell (also referred to as a shell hereinafter) of the present invention is a silver halide formed after chemical sensitization of silver halide grains forming an inner shell (hereinafter also referred to as a core) in the step of preparing an emulsion. It is a phase. The internal latent image type silver halide grains used in the present invention preferably have a core / shell structure as described above. The shell manufacturing method is described in Examples of JP-A-63-151618 and US Pat.
317,322, 3,761,276 and 4,2
69,927 and 3,367,778 can be referred to. In this case, the core / shell molar ratio (weight molar ratio) is preferably 1/30 to 5/1, more preferably 1/20 to 2/1, and further preferably 1/20 to 1
It is / 1.

For the tabular grains, Gutoff, Photographic Science and Engineering (Gutoff, Photographic Science and Engine)
ering), Vol. 14, pp. 248-257 (1970) and the like.

The method of adding pre-precipitated silver halide grains to a reaction vessel for preparing an emulsion is described in US Pat. Is more preferable. These can be used as seed crystals, and are also effective when provided as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size. As an addition method, the whole amount can be added at once, divided into a plurality of times or added continuously, or the like. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

Besides the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,
469,480, U.S. Pat. No. 3,650,757,
A particle forming method in which the concentration is changed or the flow rate is changed as described in U.S. Pat. No. 4,242,455 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied if necessary. Furthermore, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is. A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is US Pat. Nos. 2,996,287, 3,342,605, 3,415,650 and 3,785,777. , West German Published Patents 2,556,885, 2,555,364
It can be used by selecting from the methods described in No.

During the production of an emulsion containing tabular grains, a silver salt solution (eg AgN) added to accelerate grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the O ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferable. Regarding these methods, for example, British Patent No. 1,335,925 and US Pat. No. 3,672,90 are described.
0, 3,650,757, 4,242,445
No. 5, JP-A-55-142329 and JP-A-55-15812.
The description of No. 4 etc. can be referred to.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. By doping with metal ions in this way, it is possible to increase the amount of overexposure without causing re-inversion and to lower the minimum concentration. When the grains are doped, they are preferably added at the time of grain formation, when the grain surface is modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Mg, Ca, Sr, Ba, Al, Sc, Y, L
a, Cr, Mn, Fe, Co, Ni, Cu, Zn, G
a, Ru, Rh, Pd, Re, Os, Ir, Pt, A
u, Cd, Hg, Tl, In, Sn, Pb, Bi and the like can be used, but Fe, Co, Ru, Ir, Pt,
Au and Pb are preferable, and Fe, Ru, Ir and Pb are particularly preferable. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example, CdBr ₂ , CdCl ₂ ,
_{Cd (NO 3) 2, Pb} (NO 3) 2, Pb (CH 3 CO
O) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (C
N) ₆ ], K ₃ IrCl ₆ , NH ₄ RhCl ₆ , K ₄ Ru
(CN) _{6 and the} like. As a ligand of a coordination compound, halo, aco, cyano, cyanate, thiocyanate,
It can be selected from nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may use two types or a combination of three or more types.

The metal compound is preferably added after being dissolved in water or a suitable solvent such as methanol or acetone. Aqueous hydrogen halide solution (eg H 2 to stabilize the solution)
Cl, HBr, etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. In addition, a water-soluble silver salt (eg AgNO ₃ ) or an aqueous alkali halide solution (eg NaCl, KBr, K)
It can also be added to I) and continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be effective in some cases. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanate, carbonate,
Phosphate and acetate may be present. Regarding these, US Pat. Nos. 2,448,060 and 2,628,
No. 167, No. 3,737,313, No. 3,772,0
31 and Research Disclosure, 134
Vol., June 1975, 13452, etc.

The shape of tabular grains can be selected from triangles, hexagons, circles and the like. U.S. Pat. No. 4,996,1
A regular hexagon having six sides of approximately equal length as described in No. 37 is a preferable form. The tabular emulsion of the present invention is
An emulsion in which silver halide grains having an aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of 2 or more and 100 or less are present in an amount of 50% (area) or more of all silver halide grains in the emulsion. Preferably, the silver halide grains having an aspect ratio of 5 or more, more preferably 5 to 8,
The emulsion is present in an amount of 50% (area) or more of all silver halide grains in the emulsion, preferably 70% or more, and particularly preferably 85% or more. Here, the equivalent circle diameter in a tabular silver halide grain is the equivalent circle diameter of two opposing parallel or nearly parallel principal planes (diameter of a circle having the same projected area as the principal plane) and grain thickness. It represents the distance between the principal planes. Also, the aspect ratio is 100
If it exceeds the range, there is a problem that the emulsion is deformed or destroyed in the process until the emulsion is completed as a coated product, which is not preferable.

The equivalent-circle diameter of the tabular grains is 0.3 μm or more, preferably 0.3 to 10 μm, more preferably 0.
5 to 5.0 μm, more preferably 0.5 to 3.0 μm
Is. The grain thickness is less than 1.5 μm, preferably 0.0
It is 5 to 1.0 μm. Furthermore, the coefficient of variation of particle thickness is 3
Emulsions with high thickness uniformity of 0% or less are also preferable. Further, grains described in JP-A-63-163451, in which the grain thickness and the interplanar distance between twin planes are defined, are also preferable. The grain diameter and grain thickness of tabular grains can be measured by US Pat.
It can be determined by electron micrographs of particles as described in the method described in No. 34,226.

The grain size of the emulsion used in the present invention depends on the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and grain thickness, or the sphere equivalent diameter of the volume measured by the Coulter counter method. Can be evaluated. It can be selected from ultrafine particles having a sphere-equivalent diameter of 0.05 μm or less and coarse particles having a diameter of more than 10 μm. Particles of 0.1 μm or more and 3 μm or less are preferable. The grain size distribution of silver halide grains is arbitrary, but monodisperse grains are preferable. Here, monodisperse is defined as a dispersion system in which 95% of the total weight or the total number of silver halide grains contained therein falls within ± 60% of the number average grain size, preferably within 40%. It Here, the number average grain size is the number average diameter of the projected area diameters of silver halide grains. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A 63-151618.
Nos. And the like, and these monodisperse emulsions may be mixed and used.

As the silver halide composition of these grains, any one of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodide, and silver chloride is used. However, silver bromide and silver iodobromide are preferred. Further, other silver salts such as silver thiocyanate, silver cyanate, silver sulfide,
Silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains.

The silver halide grains may have different phases in the inside and the surface layer, or may have a uniform phase.
The silver halide composition in the grain may be uniform, may have a different silver halide composition between the inside and the outside, or may have a layered structure. (JP-A-57-15
No. 4232, No. 58-108533, No. 58-248.
No. 469, No. 59-48755, No. 59-52237.
U.S. Pat. Nos. 3,505,068 and 4,433.
048, 4,444,877, European Patent No. 10
0,984, and British Patent 1,027,146).
Also, particles having dislocation lines may be used.

In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a variation coefficient of 20% or less is preferable.
Another preferred form is an emulsion where there is a correlation between grain size and halogen composition.

It is important to control the halogen composition near the surface of the grain. Increase the content of silver iodide near the surface,
Alternatively, increasing the silver chloride content changes the adsorbability of the dye and the developing rate, and can be selected according to the purpose.
When changing the halogen composition in the vicinity of the surface, it is possible to select either a structure that encloses the entire grain or a structure that attaches only a part of the grain. For example, (100) plane and (11
1) The case where the halogen composition is changed only on one surface of the tetradecahedral grain composed of faces, or the halogen composition is changed on one of the main planes or side surfaces of the tabular grain.

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

In the silver halide emulsion of the present invention, it is preferable that after chemically sensitized core grains are coated with a shell, the grain surface is further chemically sensitized, but the grain surface is not chemically sensitized. I don't mind. In general, chemical sensitization on the grain surface shows good reversal performance with high maximum density. When chemical sensitization is applied to the grain surface, it is disclosed in JP-A-57-136.
A polymer as described in No. 41 may coexist. The above chemical sensitization is described by James, The Theory of the Photographic Process, 4th Edition, published by Macmillan, 1977 (TH James, The Theory o
f the Photographic Process, 4th ed., Macmillan, 1
977) 67-76 and using active gelatin, and Research Disclosure 120, April 1974, 12008; Research Disclosure, 34, 1975 6
Mon, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, 4,266. , 018, and 3,904,415.
And pAg 5-10, pH 4-8 and temperature 30-as described in GB 1,315,755.
It can be carried out at 80 ° C. with sulfur, selenium, tellurium, gold, platinum, palladium, iridium, rhodium, osmium, rhenium or combinations of these sensitizers.

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

Japanese Patent Publication No. 58-1410, Mois
ar) et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27, silver halide emulsions can reduce and sensitize the inside of grains during the precipitation formation process. . The following reduction sensitization can also be used as the chemical sensitization. U.S. Pat. No. 3,891,
As described in US Pat. No. 2,518,698 and US Pat. No. 2,743, it is possible to carry out reduction sensitization by using, for example, hydrogen.
182 and 2,743,183 with reducing agents or low pAg (eg less than 5).
Alternatively, reduction sensitization can be performed by treatment with high pH (for example, greater than 8). Stannous salt as a typical reduction sensitizer,
Ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid,
Silane compounds and borane compounds are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. Stannous chloride, thiourea dioxide as reduction sensitizer,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. U.S. Pat. No. 3,917,
The chemical sensitization methods described in No. 485 and No. 3,966,476 can also be applied.

Gelatin is advantageously used as the protective colloid used in the preparation of 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; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, A variety of synthetic hydrophilic polymeric substances such as a single or copolymer such as polyvinylpyrazole can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Photo.Japan, No.
16, an enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. Although many impurity ions are contained in gelatin, it is also preferable to use gelatin in which the amount of inorganic impurity ions is reduced by ion exchange treatment.

The emulsion of the present invention is preferably washed with water for desalting and then dispersed in a newly prepared protective colloid. The temperature of washing with water can be selected according to the purpose, but it is preferably selected in the range of 5 to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a polymer for washing with water, a method using a gelatin derivative, and the like.

In the present invention, spectral sensitization can be performed using a sensitizing dye. The sensitizing dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257,
JP-A-59-180550 and JP-A-60-140335.
No. 61-160739, RD17029 (197).
8) 12 to 13 pages, RD17643 (1978) 2
The sensitizing dyes described on page 3, etc. may be mentioned.

These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,9.
77,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
7,862, 4,026,707, British Patents 1,344,281, 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, and Japanese Patent Laid-Open No. 5-12375.
2-110618 and 52-109925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. (For example, U.S. Pat. Nos. 3,615,613, 3,
615, 641, No. 3,617, 295, No. 3, 6
35,721, 2,933,390, 3,74
3,510, those described in JP-A-63-23145, etc.). The timing of adding the sensitizing dye for spectral sensitization to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is done after the completion of chemical sensitization and before coating, but US Pat.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 58-1139.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. Furthermore, it is possible to add these said compounds separately, as taught in U.S. Pat. It can be added after the sensation, and can be added at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756.

The amount of addition is 10 mol per mol of silver halide.
It can be used in an amount of ^-8 to 10 ^-2 mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 µm, about 5 x 10 ^-5 to 2 x 10 ^-3 mol is more effective.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants and photographic stabilizers can be used for the purpose of preventing sensitivity deterioration and fogging. For example, RD17643
(1978) 24-25, U.S. Pat. No. 4,629,
Nos. 678 and azaindenes, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62. −
The acetylene compounds described in 87957 are used. In addition, phenethyl alcohol and JP-A-63
No. 257747, No. 62-272248, and 1,2-benzisothiazoline described in JP-A-1-80941.
-3-one, n-butyl, P-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole Is preferably added. For details, see European Patent No. 436,938A2,
It is described on page 150, lines 25 to 28. These additives are described in more detail in Research Disclosure.
Item17643 (1978), Item18716 (1)
1979) and Item 307105 (November 1989), and the relevant parts are summarized in the table below.

Types of Additives RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1989) 1 Chemical sensitizer page 23 648 page right column 866 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, pages 23 to 24, page 648, right column, page 866 to 868, supersensitizer, page 649, right column 4, whitening agent, page 24, page 647, page 868, page 5, page 5, page 25, page 649, right column, page 868, page 868 Page 870 Agent, stabilizer 6 Light absorber, page 25-26 Page 649 Right column Page 873 Filter-Page 650 Left column Dye, UV absorber 7 Stain 25 Page right column 650 Page Left column Page 872 Inhibitor-Right column 8 Dye image Page 25 Page 650 Left column 872 Stabilizer 9 Hardener 26 Page 651 Page left column 874 to 875 10 Binder page 26 Same as above 873 to 874 page 11 Plasticizer, Page 27 650 page Right column 876 Lubrication Agent 12 Coating aid, pages 26-27 ibid. 875-876 pages Surfactant 13 Static p. 27 pages ibid. 876-877 pages Inhibitor 14 matting agents pages 878-879

Further, the effect of the present invention is that the above-mentioned general formula [A],
It becomes more remarkable when the compound represented by [B] or [C] is used. Next, the compound represented by the general formula [A], [B], or [C] will be described in more detail.

[0039]

[Chemical 3]

When R, R ¹ and R ² are aliphatic groups, they are saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon groups, preferably alkyl groups having 1 to 22 carbon atoms,
An alkenyl group and an alkynyl group each having 2 to 22 carbon atoms, which may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl,
Pentyl, hexyl, octyl, 2-ethylhexyl,
Examples thereof include decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl and t-butyl.
Examples of the alkenyl group include allyl and butenyl. Examples of the alkynyl group include propargyl,
Butynyl is an example. The aromatic group of R, R ¹ and R ² includes a monocyclic or condensed ring aromatic group, preferably having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. These may be substituted.
The heterocyclic group for R, R ¹ and R ² includes nitrogen, oxygen,
A 3- to 15-membered ring having at least one element selected from sulfur, selenium, and tellurium and having at least one carbon atom, preferably a 3- to 6-membered ring, for example, pyrrolidine, piperidine, pyridine. , Tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole and thiadiazole ring. Examples of the substituents of R, R ¹ and R ² include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyl), an aryl group (eg, phenyl, naphthyl,
Tolyl), hydroxy group, halogen atom (eg fluorine, chlorine, bromine, iodine), aryloxy group (eg phenoxy), alkylthio group (eg methylthio, butylthio), arylthio group (eg phenylthio), acyl group (eg, Acetyl, propionyl, butyryl, valeryl), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), acylamino group (eg, acetylamino, benzoylamino), sulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino), acyloxy group (Eg, acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group, —SO ₂ SM group, and (M represents a monovalent cation) —SO ₂ R ¹ group.

As the divalent linking group represented by L,
It is an atom or atomic group containing at least one selected from C, N, S and O. Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-,
-S -, - NH -, - CO -, - SO 2 - is made of a single or combination of such. L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include the following.

[0042]

[Chemical 4]

Examples of the divalent aromatic group of L include a phenylene group and a naphthylene group. These substituents may be further substituted with the above-described substituents. M is preferably a metal ion or an organic cation. Examples of the metal ion include lithium ion, sodium ion, and potassium ion.
Examples of the organic cation include ammonium ion (ammonium, tetramethylammonium, tetrabutylammonium, etc.), phosphonium ion (tetraphenylphosphonium), and guanidyl group. When the general formulas [A] to [C] are polymers, examples of the repeating units are as follows.

[0044]

[Chemical 5]

These polymers may be homopolymers or copolymers with other copolymerizable monomers. The compounds of the general formulas [A], [B] and [C] are disclosed in
4-1019; British Patent 972, 211; Journal of O
rganic Chemistry (Journal of Organic
Chemistry, 53, 396 (1988) and Chem.
ical Abstracts, Volume 59,
It can be easily synthesized by the method described or cited in 9776e. The compound represented by the general formula [A], [B] or [C] is 10 ⁻⁷ to 10 ⁻¹ per mol of silver halide.
It is preferable to add them in moles. Further, the addition amount of 10 ⁻⁷ to 10 ⁻³ , particularly 10 ⁻⁶ to 10 ⁻⁴ mol / mol Ag is preferable. In order to add the compounds represented by the general formulas [A] to [C] during the manufacturing process, a method usually used when adding an additive to a photographic emulsion can be applied. For example, a water-soluble compound is prepared as an aqueous solution having a suitable concentration, and a water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters, amides, etc. Among them, it can be dissolved in a solvent that does not adversely affect photographic characteristics and added as a solution. The compounds represented by the general formulas [A] to [C] are required to be present in the step of forming an outer shell during the grain formation of the silver halide emulsion, and before the formation of the outer shell is started. If it is the stage of, it may be added at any stage during the production. Preferred is a method in which the compound is added during the chemical sensitization of the inner shell (core). Further, the compounds [A] to [C] are previously added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide.
May be added in advance to form particles using these aqueous solutions. In addition, the compound [A]-
It is a preferable method to add the solution of [C] in several times or continuously for a long time. The most preferable compound of the present invention has the general formula [A]. Specific examples of the compound represented by the general formula [A], [B], or [C] are shown below, but the effects of the present invention are not limited to these compounds.

[0046]

[Chemical 6]

[0047]

[Chemical 7]

[0048]

[Chemical 8]

[0049]

[Chemical 9]

[0050]

[Chemical 10]

[0051]

[Chemical 11]

[0052]

[Chemical 12]

[0053]

[Chemical 13]

[0054]

[Chemical 14]

[0055]

[Chemical 15]

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

B) Image Receiving Layer The dye image receiving layer used in the present invention comprises a hydrophilic colloid containing a mordant. This may be a single layer or may have a multi-layered structure in which mordants having different mordant strengths are applied in layers. Regarding this, JP-A-61-25255
1 is described. As the mordant, a polymer mordant is preferable. Polymer mordants are polymers containing secondary and tertiary amino groups, polymers with nitrogen-containing heterocyclic moieties,
And a polymer containing a quaternary cation and having a molecular weight of 5,
000 or more, particularly preferably 10,000 or more. The coating amount of the mordant is generally 0.5 to 1.
0 g / m ² is preferably particularly preferably 1.0 to 5.0 g / m ² is 2 to 4 g / m ^2. As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and the like are used, and gelatin is preferable. In the image receiving layer, Japanese Patent Publication No. Sho 62-3
0620 and 62-30621, and JP-A-62-21.
The anti-fading agent described in No. 5,272 can be incorporated.

C) White Reflective Layer The white reflective layer forming the white background of the color image usually contains a white pigment and a hydrophilic binder. As the white pigment for the white reflective layer, barium sulfate, zinc oxide, barium stearate,
Silver flakes, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, titanium dioxide and the like are used. Further, non-film-forming polymer particles made of styrene or the like are also used. Further, these may be used alone or may be mixed and used within a range capable of obtaining a desired reflectance. A particularly useful white pigment is titanium dioxide. The whiteness of the white reflective layer is
Although it depends on the type of pigment, the mixing ratio of the pigment and the binder, and the coating amount of the pigment, the light reflectance is preferably 70% or more. Generally, the greater the amount of pigment applied, the better the whiteness, but as the imaging dye diffuses through this layer, the pigment resists the diffusion of the dye,
It is desirable to have an appropriate coating amount. Titanium dioxide 5
-40 g / m ² , preferably 10-25 g / m ² applied,
A white reflective layer having a light reflectance of 78 to 85% at a wavelength of 540 mm is preferred. Titanium dioxide can be selected from various commercially available brands and used. Among these, it is particularly preferable to use rutile type titanium dioxide. Most of the commercially available products are surface-treated with alumina, silica, zinc oxide or the like, and in order to obtain a high reflectance, the surface treatment amount is preferably 5% or more. Examples of commercially available titanium dioxide include Ti-pure R931 manufactured by DuPont, and those described in Research Disclosure No. 15162. As the binder of the white reflective layer, an alkali-permeable polymer matrix such as gelatin,
Polyvinyl alcohol and hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethyl cellulose can be used. A particularly preferred binder for the white reflective layer is gelatin. The ratio of white pigment to gelatin is 1 / 1-
20/1 (weight ratio), preferably 5/1 to 10/1 (weight ratio). In the white reflective layer, Japanese Examined Patent Publication Sho 62-306
It is preferable to incorporate an anti-fading agent such as No. 20 and No. 62-30621.

D) Light-shielding layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder may be provided between the white reflective layer and the photosensitive layer. As a light-shielding agent,
Although any material having a light-shielding function can be used, carbon black is preferably used. Also, US Patent No. 4,
Decomposable dyes described in 615,966 and the like may be used. The binder for coating the light-shielding agent may be any as long as it can disperse carbon black, and gelatin is preferable. Examples of carbon black raw materials include Donnel Voet "Carbon Black" Marcel Dekker, Inc.
Any manufacturing method such as a channel method, a thermal method and a furnace method as described in (1976) can be used. The particle size of carbon black is not particularly limited, but is preferably 90 to 1800. The addition amount of the black pigment as the light-shielding agent may be adjusted depending on the sensitivity of the light-sensitive material to be shielded, but it is preferably about 5 to 10 in terms of optical density.

E) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming substance is provided above the light shielding layer. The constituent elements will be described below. (1) Dye image-forming substance The dye image-forming substance used in the present invention is a non-diffusible compound which releases a diffusible dye (may be a dye precursor) in connection with silver development, or its own diffusivity. Is changing, and "the theory of photographic process" (The The
ory of the Photographic Process) 4th edition. All of these compounds can be represented by the following general formula [I]. General formula [I] (DYE-Y) _n -Z {DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like structure. To produce a difference in the diffusivity of the compound represented by (DYE-Y) _n -Z corresponding to or opposite to the photosensitive silver salt having a latent image, or to release DYE and release the DYE. And (DYE-Y) _n -Z represent a group having a property of causing a difference in diffusibility, n represents 1 or 2, and when n is 2, two DYE-Y are the same. But it can be different. } According to the function of Z, it is roughly classified into a negative compound that becomes diffusible in the silver developed area and a positive compound that becomes diffusible in the undeveloped area. Specific examples of the negative Z include those that are oxidized as a result of development and cleaved to release a diffusible dye.
Specific examples of Z include U.S. Pat. Nos. 3,928,312 and 3,9.
93,638, 4,076,529, 4,15
No. 2,153, No. 4,055,428, No. 4,05
3,312, 4,198,235, 4,17
9,291, 4,149,892, 3,84
4,785, 3,443,943, 3,75
1,406, 3,443,939, 3,44
3,940, 3,628,952, 3,98
0,479, 4,183,753, 4,14
2,891, 4,278,750, 4,13
9,379, 4,218,368 and 3,42
1,964, 4,199,355, 4,19
9,354, 4,135,929, 4,33
6,322, 4,139,389, JP-A-53-
No. 50736, No. 51-104343, No. 54-13.
0122, 53-1108827, 56-126
No. 42, No. 56-16131, No. 57-4043,
57-650, 57-20735, 53-6.
No. 9033, No. 54-130927, No. 56-164
No. 342, 57-119345 and the like.
Among Zs of the negative type dye-releasing redox compound, a particularly preferable group is an N-substituted sulfamoyl group (the N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). Representative examples of Z are shown below, but the present invention is not limited thereto.

[0061]

[Chemical 16]

Regarding the positive type compounds, Angevante Chemie International Edition English (Angev.Chem.Int.Ed.Engl.), 22, 191
(1982). Specific examples thereof include compounds (dye developers) that are initially diffusible under alkaline conditions, but are oxidized by development to become non-diffusible. As Y effective for this type of compound, US Pat.
The ones listed in No. 3606 are typical. Another type is a type in which a diffusible dye is released by self-ring closure under an alkaline condition, but the dye is not substantially released when it is oxidized during development. Specific examples of Y having such a function include U.S. Pat. No. 3,980,479, JP-A Nos. 53-69033 and 54-130927, and U.S. Pat. No. 3,421,964.
No. 4,199,355 and the like. Another type is one that does not itself release a dye but releases a dye when reduced. This type of compound can be used in combination with an electron donor to release the diffusible dye imagewise by reaction with the remaining electron donor which is imagewise oxidized by silver development. Regarding the atomic group having such a function, for example, US Pat.
3,753, 4,142,891, 4,27
8,750, 4,139,379, 4,21
8,368, JP-A-53-1108827, U.S. Pat. Nos. 4,278,750, 4,356,249, 4,358,535, and JP-A-53-1108827.
54-130927, 56-164342, Technical Report 87-6199, European Patent Publication 220746A.
No. 2 etc. Specific examples thereof will be illustrated below, but the present invention is not limited thereto.

[0063]

[Chemical 17]

When this type of compound is used, it is preferably used in combination with a diffusion-resistant electron donating compound (known as ED compound) or its precursor. Examples of ED compounds include, for example, US Pat.
263,393, 4,278,750, JP-A-5
6-138736 and the like. The following can also be used as specific examples of another type of dye image-forming substance.

[0065]

[Chemical 18]

Details of this are described in US Pat. Nos. 3,719,489 and 4,098,783. On the other hand, specific examples of the dye represented by the above general formula DYE are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. , 383, 4,195,992, 4,148,641, 4,148,643, 4,336,322: JP-A-51-114930.
56-71072: Research Disclosure 1763.
No. 0 (1978) and No. 16475 (1977). Examples of magenta dyes: U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308, and 3,954. , 476, 4,233,237, 4,255,509, 4,250,246, 4,142,891, 4,207,104, 4,287,292. Issue: JP-A-52-106,727
No. 53, No. 53, 628, No. 55-36, 804
No. 56-73,057, No. 56-71060,
Those described in No. 55-134. Examples of cyan dyes: US Pat. Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220 and 4,242. , 435, 4,142,891, 4,195,994, 4,147,544, 4,148,642; British Patent 1,551,138.
Nos. 54-99431 and 52-8827.
No. 53-47823, No. 53-143323, No. 5
4-99431, 56-71061; European Patents (EP) 53,037, 53,040; Rese
those described in arch Disclosure 17,630 (1978) and 16,475 (1977). These compounds are disclosed in JP-A-62-215,272, 14
It can be dispersed by the method described on pages 4-146. Further, these dispersions include those disclosed in JP-A-62-215,272.
No. 137-144 may be included.

(2) Silver Halide Emulsion In the present invention, the following internal latent image type direct positive silver halide emulsions having various shapes are used in combination with the above-mentioned tabular internal latent image type direct positive silver halide emulsion. be able to. As an example, those having a regular crystal form such as a cube, octahedron, tetradecahedron and rhombic dodecahedron, and those having an irregular crystal form such as a sphere and a plate, One having the following plane ((hk1) plane), or a mixture of grains of these crystal forms can be mentioned. For particles with higher order, see Journal of Imaging
Science (Journal of Imaging Science), 30th
Vol. 1986, pages 247-254. The silver halide grains used in the present invention, even if they are normal crystals that do not contain twin planes, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photography (Corona Publishing Co.), p. 163, for example, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected and used from multiple twins and the like according to the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected if necessary. In the case of normal crystal, a cube consisting of (100) plane, (11
An octahedron composed of 1) planes is disclosed in JP-B-55-42737 and JP-A-60-222842 (110).
A dodecahedral grain composed of planes can be used. Furthermore, Journal of Imaging Science, Volume 30, 247.
(211) representative (hl1) plane grains, (331) representative (hh1) face grains, and (210) plane representative (hk) as reported in 1986.
Although the (hk1) plane particles represented by the (0) plane grains and the (321) plane are required to be devised in the preparation method, they can be selected and used according to the purpose. Tetrahedral grains in which (110) plane and (111) plane coexist in one grain, (100) plane and (110) plane
Particles whose faces coexist, or (111) faces and (110) faces
Particles in which two surfaces or a large number of surfaces coexist, such as particles in which surfaces coexist, can be selected and used according to the purpose.

The silver halide composition of these grains and the grain size of the emulsion can be selected from those similar to the tabular internal latent image type direct positive silver halide emulsion described above.

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64412B1, or West German Patent No. 2,306,447C2. , JP Sho 60
The surface may be modified as disclosed in US Pat. A structure having a flat particle surface is generally used, but intentionally forming irregularities is sometimes preferable. JP-A-58-106532, 60-22132
Part of the crystals described in US Pat. No. 0, for example, a method of drilling holes in the centers of vertices or planes, or US Pat.
Raffle particles described in 643,966 are examples.

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

The silver halide grains described above are based on Research Disclosure (RD) No. 17643 (19
Dec. 1978, pp. 22-23, "I. Emulsion production (Emul
sionpreparation and types) ”and ibid. No. 1871
6 (November 1979), p. 648, ibid. 30710
5 (November 1989), pages 863-865, and "Graphics and Chemistry" by Graphide, published by P.Glafkides Chimie et Pysique Photograhique, Paul.
Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emuls).
ion Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VLZelikman et al, Making and Coating Photograp
hic 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 halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The above-described normal crystal silver halide grains can be obtained by controlling pAg and pH during grain formation. For details, see, for example, Photographic Scien
ce and Engineering), Volume 6, 159-165 (1
962); Journal of Photographic Science, 12
Vol. 242-251 (1964), U.S. Pat. No. 3,6.
55,394 and British Patent 1,413,748. Regarding monodisperse emulsions, JP-A-48-8600, JP-A-51-39027 and JP-A-51-8.
No. 3097, No. 53-137133, No. 54-485.
21, No. 54-99419, No. 58-37635.
No. 58-49938, Japanese Patent Publication No. 47-11386
No. 3,655,394 and British Patent No. 1,413,748.

A method for converting most or only a part of the halogen composition of silver halide grains by the halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,14.
2,900, European Patents 273,429, 273.
No. 430 and West German Laid-Open Patent No. 3,819,241 and the like, which is an effective particle forming method. A solution of soluble halogen or silver halide grains can be added to convert it to a more sparingly soluble silver salt. It is possible to select from a method such as conversion at once, conversion by dividing into plural times, or continuous conversion.

Besides the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,
469,480, U.S. Pat. No. 3,650,757,
A particle forming method in which the concentration is changed or the flow rate is changed as described in U.S. Pat. No. 4,242,455 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time.

Similar to the above-mentioned tabular internal latent image type direct positive silver halide emulsion, a metal ion salt is present during the above emulsion preparation, for example, during grain formation, desalting step, chemical sensitization, and before coating. It is preferable to do so according to the purpose. The method of adding a chalcogenide compound as described in U.S. Pat. No. 3,772,031 during preparation of an emulsion may be effective in some cases.

The internal latent image type silver halide grains used in the present invention preferably have a core / shell structure as described above. Shell production method, after coating the shell to the core particles chemically sensitized, a method of chemically sensitizing the particle surface,
Further, regarding chemical sensitization in the presence of a chemical sensitization auxiliary agent, reduction sensitization, or sensitization method using an oxidizing agent, etc., the same as in the above-mentioned tabular internal latent image type direct positive silver halide emulsion. It can be carried out.

Selection of protective colloid, washing method for desalting, spectral sensitization method using a sensitizing dye, various antifoggants and photographic stabilizers for the purpose of preventing sensitivity deterioration and fogging. It can be used in the same manner as the above-mentioned tabular internal latent image type direct positive silver halide emulsion.

(3) Construction of Photosensitive Layer For the reproduction of natural color by the subtractive color method, the dye which provides a dye having a selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the above spectral sensitizing dye. A photosensitive layer consisting of at least two layers with an image-forming substance is used. The emulsion and the dye image-forming substance may be coated as separate layers,
Alternatively, they may be mixed and coated as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity region of the emulsion combined with it, another layer is preferable. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image-forming substance layer. For example, a layer containing a nucleation development accelerator described in JP-A-60-173541, JP-B-60-1
The partition layer described in No. 5267 can be provided to increase the color image density, and a reflective layer can be provided to increase the sensitivity of the photosensitive element. The reflective layer is a layer containing a white pigment and a hydrophilic binder, preferably the white pigment is titanium oxide and the hydrophilic binder is gelatin. The amount of titanium oxide applied is 0.1 g / m ^{2 to} 8 g / m ² , preferably 0.1.
It is a ^{2g / m 2 ~4g / m 2} . Examples of the reflective layer are described in JP-A-60-91354. In a preferable multilayer structure, a combination unit of blue-sensitive emulsion, a combination unit of green-sensitive emulsion and a combination unit of red-sensitive emulsion are sequentially arranged from the exposure side. An arbitrary layer can be provided between each emulsion layer unit as needed. In order to prevent the unfavorable influence of the development effect of one emulsion layer on other emulsion layer units,
It is preferable to provide a color mixing prevention layer. When the developer is used in combination with the non-diffusible dye image forming substance, the color mixing prevention layer preferably contains a non-diffusible reducing agent in order to prevent diffusion of the oxidized product of the developer. Specific examples thereof include non-diffusible hydroquinone, sulfonamide phenol, sulfonamide naphthol, and the like, and more specifically, JP-B Nos. 50-21249, 50-23813, and JP-A No. 4-23813.
9-106329, 49-129535, US Pat. Nos. 2,336,327, 2,360,290, 2,403,721, 2,544,640 and 2,732,300. Nos. 2,782,659, 2,937,086, 3,637,393, 3,700,453, British Patent 557,750, JP-A-57-24941, and JP-A-57-24941. 58-21249 and the like. In order to prevent undesired migration of these reducing agents to the emulsion layer and to control the activity as a reducing agent, it is preferable to disperse them together with the polymer. Preferable polymers include polyvinyl acetic acid, polymethyl methacrylate, polyacrylamide derivatives and the like.
Regarding their dispersion method, JP-A-60-238831
No. 60-18978. When a compound which releases a diffusible dye by silver ion as described in JP-B-55-7576 is used, it is preferable to include a compound which complements silver ion in the color mixture preventing layer. In the present invention, an anti-irradiation layer, a UV absorber layer, a protective layer, etc. may be coated as necessary. Further, a partition layer made of gelatin may be provided between any adjacent layers, if necessary.

In order to prevent fog and adjust photographic gradation, a development inhibitor pre-curer, a diffusion resistant reducing agent and the like can be incorporated in any of the above-mentioned photosensitive layers.

As the hydrophilic binder used in the photosensitive layer, any hydrophilic binder can be used as long as it can permeate the processing liquid and transfer the image dye. For example, gelatin, polyacrylamide, polyvinyl alcohol, or their derivatives can be used. The hydrophilic binder may be hardened by a hardener, and 0.5% to 5%, preferably 0.5 to 2% of the hydrophilic binder is added.

F) Peeling Layer In the present invention, a peeling layer may be provided for peeling off the photosensitive sheet in the unit at any place after processing, if necessary. Therefore, this peeling layer must be easy to peel off after the treatment. As a material for this, for example,
JP-A-47-8237, JP-A-59-220727, JP-A-59-229555, JP-A-49-4653, US Pat. Nos. 3,220,835, 4,359,518, and JP-A-49-4334. No. 56, No. 56-65133, No. 45
-24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 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 so on. Another example is various natural polymers such as alginic acid, pectin, and gum arabic.
Also various modified gelatins such as acetylated gelatin,
Phthalated gelatin is also used. Yet another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethylmethacrylate, polybutylmethacrylate, or a copolymer thereof may be used. The release layer can be a single layer,
Further, for example, JP-A-59-220727 and JP-A-60-6.
It may be composed of a plurality of layers as described in No. 0642.

II. Cover Sheet In the present invention, a layer having a neutralizing function (neutralizing layer and timing of neutralization) is provided in order to uniformly spread the processing liquid on the photosensitive element, neutralize the alkali after processing, and stabilize the image. A transparent cover sheet with layers).

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

H) Layer Having Neutralizing Function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize an alkali carried from the treatment composition, and if necessary, Accordingly, it may have a multi-layered structure including layers such as a neutralization rate adjusting layer (timing layer) and an adhesion enhancing layer. The preferred acidic substance is a substance containing an acidic group having a pKa of 9 or less (or a precursor group which gives such an acidic group by hydrolysis), more preferably oleic acid described in US Pat. No. 2,983,606. Higher fatty acids such as US Pat. No. 3,362,819
Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides as disclosed in US Pat. No. 2,290,699; acrylic acid and acrylic acid as disclosed in French Patent 2,290,699. Ester isotopes;
No. 4,139,383 or Research Disclosure No. 16102 (19
Mention may be made of latex-type acidic polymers as disclosed in 77). Others, US Patent 4,08
8,493, JP-A-52-153,739, 53
-1, 023, 53-4, 540, 53-4,
The acidic substances disclosed in No. 541, No. 53-4, 542 and the like can also be mentioned. Specific examples of the acidic polymer include copolymers of vinyl monomers such as ethylene, vinyl acetate and vinyl methyl ether with maleic anhydride, and their n-
Examples thereof include butyl ester, a copolymer of butyl acrylate and acrylic acid, cellulose, acetate / hydrogen phthalate. The polymer acid can be used as a mixture with a hydrophilic polymer. Such polymers include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polymethyl vinyl ether and the like. Of these, polyvinyl alcohol is preferable. Further, a polymer other than the hydrophilic polymer, such as cellulose acetate, may be mixed with the polymer acid. The coating amount of the polymer acid is adjusted by the amount of alkali spread on the photosensitive element. The equivalent ratio of polymer acid and alkali per unit area is preferably 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stains are generated on the white background portion, and if it is too large, the hue is changed or the light resistance is deteriorated. A more preferable equivalent ratio is 1.0 to 1.3. If too much or too little hydrophilic polymer is mixed, the quality of the photograph will be degraded. The weight ratio of hydrophilic polymer to polymeric acid is 0.1 to 10, preferably 0.3 to 3.
It is 0. Additives can be incorporated into the layer having a neutralizing function of the present invention for various purposes. For example, hardening agents well known to those skilled in the art for hardening this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. for improving the brittleness of the film can be added. In addition, if necessary, an antioxidant, a fluorescent brightening agent, a development inhibitor and a precursor thereof may be added. 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, partially hydrolyzed polyvinyl acetate,
Polymers that lower alkali permeability such as; 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 Is. Among them, JP-A-54-1363
28, U.S. Pat. Nos. 4,267,262 and 4,00
Timing layers using cellulose acetate disclosed in JP-A-9,030 and JP-A-4,029,849;
4-128335, 56-69, 629, 57
-6,843, U.S. Pat. Nos. 4,056,394, 4,061,496, 4,199,362, 4,250,243, 4,256,827, and 4, respectively. Latex polymers disclosed in U.S. Pat. No. 4,229,516, which are disclosed in U.S. Pat. No. 4,229,516, and which are disclosed in U.S. Pat. No. 4,229,516; KAISHO 56-25735, 56-97346, 57-
6842, European Patent (EP) 31,957A1
The polymers disclosed in Nos. 37,724A1 and 48412A1 are particularly useful. In addition, those described in the following documents can also be used. US Patent 3,42
1,893, 3,455,686, 3,57
5,701, 3,778,265, 3,78
No. 5,815, No. 3,847,615, No. 4,08
8,493, 4,123,275, 4,14
8,653, 4,201,587, 4,28
8,523, 4,297,431, West German Patent Application (OLS) 1,622,936, 2,162,27
No. 7, Research Disclosure 15162, No. 151
(1976). The timing layer using these materials may be used alone or in combination of two or more layers.
Further, for the timing layer made of these materials, for example, US Pat. No. 4,009,029, West German patent application (OLS)
No. 2,913,164, No. 3,014,672, JP-A Nos. 54-155837 and 55-138745, and their development inhibitors and / or their precursors; and US Pat. It is also possible to incorporate the hydroquinone precursors disclosed in No. 201,578, other useful photographic additives or their precursors. Further, as a layer having a neutralizing function, JP-A-63-168648 and 63-16864 are available.
Providing an auxiliary neutralizing layer as described in No. 9 is effective in reducing the change in transfer density over time after the treatment.

I) Others In addition to the layer having a neutralizing function, a back layer, a protective layer, a filter dye layer and the like may be provided as a layer having an auxiliary function. The back layer is provided for adjusting curl and imparting slipperiness. Filter dyes may be added to this layer. In the mono-sheet type photosensitive material, the protective layer is mainly used to prevent adhesion to the back surface of the cover sheet and adhesion of the photosensitive material protective layer when the photosensitive material and the cover sheet are superposed. The capture mordant layer can prevent the delay of the image completion time and the deterioration of the sharpness by capturing the dye diffused to the alkali treatment composition side.
Usually, a dye capturing layer is provided on the outermost layer of the cover sheet. The dye capturing layer contains a polymer mordant in a hydrophilic colloid as in the dye image receiving layer described above.
No. 8747 and JP-A-2-282253. The cover sheet may contain a dye to adjust the sensitivity of the photosensitive layer. The filter dye may be added directly to the support of the cover sheet or a layer having a neutralizing function, and further to the above back layer, protective layer, capture mordant layer, or the like,
You may install a single layer.

III. Alkali 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. Therefore, in the composition, an alkali, a thickener, a developing agent, a development accelerator for controlling the development, a development inhibitor, an antioxidant for preventing the deterioration of the developing agent, a gradation It contains a regulator, etc.
Alkali is sufficient to adjust the pH of the liquid to 12 to 14, and alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide, lithium hydroxide), alkali metal phosphates (eg potassium phosphate). , Guanidines,
Examples thereof include hydroxides of quaternary amines (for example, tetramethylammonium hydroxide), of which potassium hydroxide and sodium hydroxide are preferable, and potassium hydroxide is particularly preferable. The thickener is used to spread the treatment liquid uniformly.
It is also necessary to maintain the close contact between the photosensitive layer and the cover sheet. For example, polyvinyl alcohol, hydroxyethyl cellulose, an alkali metal salt of carboxymethyl cellulose is used, but to prevent liquid leakage from the rupturable container of the processing liquid, and to uniformly spread on the photosensitive layer at the time of spreading, thixotropic property. Preferred are hydroxyethyl cellulose, sodium hydroxymethylcarboxylate, and carboxymethyl-hydroxyethyl cellulose.

As the preferred developing agent, any developing agent can be used as long as it cross-oxidizes the dye image-forming substance and does not substantially produce stain even when it is oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor type. These developers may be included in the appropriate layers of the light sensitive element or in the alkaline processing liquid. Specific examples of the compound include aminophenols and pyrazolidinones. Of these, pyrazolidinones are particularly preferable because they generate less stain. For example, 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3'-methyl-phenyl) -4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidinone,
And so on.

Development accelerators include amines, amino acids,
Other than polyethylene glycols, benzyl alcohol,
Dihydroxymethylbenzene or the like is used. Although any development inhibitor can be used, a triazole derivative is preferable for development of an autopositive emulsion combined with a nucleating agent, and a benztriazole derivative is particularly preferable. As the antioxidant for preventing the deterioration of the developing agent, any one having a reducing power for preventing the oxidation of the developing agent is used, but sulfite, particularly potassium sulfite is preferably used. As the gradation control agent, hydroquinone derivatives and ascorbic acid derivatives are preferably used. In addition, in order to improve the temporal stability of the treatment liquid,
It is also preferable to add a transition metal salt such as zinc nitrate, or to add an aluminum salt for imparting pH buffering property.

A light-shielding agent can be contained in the treatment liquid, if necessary. Particularly, in the case of an integral type photosensitive material which is exposed through a transparent support, it is necessary to impart a light-shielding property to the processing liquid. Carbon black and other pigments and dyes can be used as the light-shielding agent therefor. In particular, when the treatment liquid contains a white pigment and a dye image is observed against the developed treatment liquid layer, it is preferable to use a pH-sensitive dye as a light-shielding agent.

The development accelerator described on pages 72 to 91 of JP-A-62-215272, the film hardener described on pages 146 to 155, the composition described on pages 201 to 210 in any of the light-sensitive sheet, the cover sheet or the alkaline processing composition. Surfactant, 210
To a 222-page fluorine-containing compound, 225-227 page thickener, 227-230 page antistatic agent, 23
The polymer latex described on page 0 to 239, the matting agent described on page 240, and the like can be included.

[0091]

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. The following four types of silver halide emulsion grains (Emulsion-A to Emulsion-C) and Emulsion-D7 were prepared by the following emulsion grain preparation methods.
Was prepared.

Preparation of Emulsion-A (octahedral internal latent image type direct positive emulsion): 0.05M potassium bromide, 1 g of 3,6-dithia-1,8-octanediol, 0.05 mg of lead acetate and 100 ppm of Ca content. 60 g of the following deionized gelatin
In a gelatin aqueous solution (1000 ml) containing
While maintaining at ℃, 0.4M silver nitrate aqueous solution and 0.4M potassium bromide aqueous solution were controlled by double jet method.
300 ml of an aqueous silver nitrate solution was added over 40 minutes while controlling the addition rate of the aqueous potassium bromide solution such that Br was 1.60. When the addition was completed, octahedral silver bromide crystals (hereinafter referred to as core particles) having a uniform particle size with an average particle size (equivalent sphere diameter) of about 0.7 μm were produced. Next, 1 mg of sodium thiosulfate, 90 mg of potassium tetrachloroaurate and 3 g of an aqueous solution of 1.2 g of potassium bromide dissolved in 1000 ml of water were added to this prepared solution, and the mixture was heated at 75 ° C. for 80 minutes for chemical sensitization treatment. I went. After 0.15M potassium bromide was added to the emulsion solution chemically sensitized in this way, 0.9M silver nitrate aqueous solution and 0.9M silver nitrate aqueous solution were added while maintaining the temperature at 75 ° C as in the case of preparing core particles. 670 ml of an aqueous silver nitrate solution was added over 70 minutes while the addition rate of the aqueous potassium bromide solution was adjusted by the control double jet method so that the pBr was 1.30. This emulsion was washed with water by a conventional flocculation method, and the above-mentioned gelatin, 2-phenoxyethanol, and methyl P-hydroxybenzoate were added to obtain an average particle size (equivalent sphere diameter) of about 1.4 μm. Octahedral silver bromide crystals (hereinafter referred to as internal latent image type core / shell grains)
Got Next, to this internal latent image type core / shell emulsion, 3 ml of an aqueous solution of 100 ml of sodium thiosulfate and 40 mg of sodium tetraborate dissolved in 1000 ml of water was added, and further 14 mg of poly (N-vinylpyrrolidone) was added and heated at 60 ° C. After ripening, an octahedral internal latent image type direct positive emulsion was prepared by adding 0.005 M potassium bromide.

Preparation of emulsion-B (octahedral internal latent image type direct positive emulsion): In the preparation method of emulsion-A, the addition time of the aqueous solution of silver nitrate and the aqueous solution of potassium bromide was changed, and further the amount of added chemicals was changed. The average particle size (sphere equivalent diameter) is about 1.
An octahedral internal latent image type direct positive emulsion having a uniform grain size of 0 μ was obtained.

Preparation of emulsion-C (octahedral internal latent image type direct positive emulsion): In the preparation method of emulsion-A, the addition time of the silver nitrate aqueous solution and the potassium bromide aqueous solution was changed, and further the amount of added chemicals was changed. The average particle size (equivalent sphere diameter) is about 0.
An octahedral internal latent image type direct positive emulsion having a uniform grain size of 7 μm was obtained.

Emulsion-D6 (hexagonal tabular internal latent image type direct positive emulsion) preparation: potassium bromide 0.05M, average molecular weight 1
1.4M containing the above gelatin in 1.2 liters of gelatin aqueous solution containing 0.7% or less of gelatin by 0.7% by weight.
33 ml of each of them was simultaneously mixed by the double jet method for 1 minute while vigorously stirring the silver nitrate aqueous solution (2) and the 2M potassium bromide aqueous solution. During this period, the gelatin aqueous solution was kept at 30 ° C. Further, 300 cc of a gelatin solution containing 10% by weight of deionized gelatin having a Ca content of 100 ppm or less was added, and the temperature was raised to 75 ° C. Next, 0.9M silver nitrate aqueous solution 40cc
Was added over 3 minutes, 25% by weight aqueous ammonia solution was added, and the mixture was aged at 75 ° C. After completion of the ripening, after neutralizing the ammonia, 5 ml of lead acetate (added with an aqueous solution) was added, and an accelerated flow rate of 1M silver nitrate aqueous solution and 1M potassium bromide aqueous solution was used while keeping pBr at 2.2 (at the end The flow rate was 6 times the flow rate at the start), and the addition was carried out by the double jet method. (The amount of the aqueous silver nitrate solution used was 500 cc.) The particles thus formed (hereinafter referred to as core particles) were washed with water by a conventional flocculation method to obtain gelatin, 2-phenoxyethanol and P-hydroxybenzoic acid. Methyl acid was added to obtain 750 g of hexagonal tabular core particles. The obtained hexagonal tabular core particles have an average projected area circle equivalent diameter of 0.9 μm and an average thickness of 0.20 μm,
Hexagonal tabular grains accounted for 95% of the total projected area. Next, 200 g of the hexagonal tabular core emulsion is mixed with 13 parts of water.
00 ml, potassium bromide 0.11M and deionized gelatin 4
After adding 0 g and raising the temperature to 75 ° C., 3,6-dithia-
0.3 g of 1,8-octanediol, 10 mg of Compound 1-16, 2.4 ml of an aqueous solution prepared by dissolving 90 mg of potassium tetrachloroaurate and 1.2 g of potassium bromide in 1000 ml of water, and 15 mg of lead acetate (in an aqueous solution). Add) and add at 75 ° C for 1
The chemical sensitization treatment was performed by heating for 80 minutes. Next, the outer shell is formed. In the same manner as in the preparation of the core particles, the core particles chemically sensitized in this way were treated with a 2M silver nitrate aqueous solution and a 2.5M potassium bromide aqueous solution with a pBr of 2.
While adjusting the addition amount and the addition rate of the potassium bromide aqueous solution to be 2, the double jet method was added at an accelerated flow rate (the flow rate at the end was 3 times the flow rate at the start).
(The amount of the aqueous silver nitrate solution used was 810 cc.) After adding 0.3 M potassium bromide, this emulsion was washed with water by a conventional flocculation method and gelatin was added. Thus, a hexagonal tabular internal latent image type core / shell emulsion was obtained. The obtained hexagonal tabular grains have an average projected area circle equivalent diameter of 2.5 μm and an average thickness of 0.37 μm.
88% of the total projected area with an average volume size of 1.4 (μm) ³
Were occupied by hexagonal tabular grains. Next, 100 mg of sodium thiosulfate and 40 mg of sodium tetraborate were added to 1000 parts of water in the hexagonal tabular internal latent image type core / shell emulsion.
A hexagonal tabular internal latent image type direct positive emulsion was prepared by adding 15 ml of an aqueous solution dissolved in 20 ml and further adding 20 mg of poly (N-vinylpyrrolidone) and chemically sensitizing the grain surface by heating at 60 ° C. for 100 minutes. Was prepared.

Emulsion-D1 to Emulsion-Emulsion for D5-
In D6, the addition amount and the addition rate of the potassium bromide aqueous solution at the time of forming the outer shell (shell) are adjusted, and further the general formula [A],
It was prepared by adjusting the addition amount of a compound selected from [B] and [C]. The preparation methods are shown in Table 1 as a list.

[0097]

[Table 1]

Using these emulsions, a comparative photosensitive element (Sample 101) having the constitution shown in Table 2 below was prepared.

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

[Table 4]

[0102]

[Table 5]

[0103]

[Table 6]

[0104]

[Table 7]

[0105]

[Table 8]

[0106]

[Chemical 19]

[0107]

[Chemical 20]

[0108]

[Chemical 21]

[0109]

[Chemical formula 22]

[0110]

[Chemical formula 23]

Next, the emulsions of the eighth layer, the fifteenth layer and the twenty-second layer were sequentially replaced by emulsion-D1 to emulsion-D6 as shown in Table 4, to prepare samples 201 to 206.

[0112]

[Table 9]

The cover sheet was prepared as follows. The following layers were coated on a polyethylene terephthalate transparent support containing a gelatin-primed anti-light piping dye. (1) 10.4 g / m ^{2 of} an acrylic acid-butyl acrylate (molar ratio 8: 2) copolymer having an average molecular weight of 50,000 and 1,
4-bis (2,3-epoxypropoxy) -butane 0.
Neutralization layer containing 1 g / m ² . (2) Acetyl cellulose with an acetylation degree of 51% 4.3 g / m ² ,
A neutralization timing layer containing 0.2 g / m ² of poly (methyl vinyl ether-co-monomethyl maleide). (3) Styrene-butyl acrylate-acrylic acid-N methylol acrylamide in a weight ratio of 49.7 / 42.3 /
The polymer latex obtained by emulsion polymerization at a ratio of 4/4 and the polymer latex obtained by emulsion polymerization of methyl methacrylate / acrylic acid / N-methylol acrylamide at a weight ratio of 93: 3: 4 have a solid content ratio of 6: 4. Blended as described above and containing 2.5 g / m ^{2 of} total solid content. (4) A layer containing 1 g / m ² of gelatin.

The alkaline treatment composition was prepared by the following method. 0.8 g of a treatment liquid having the following composition was filled in a container that can be destroyed by pressure. 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10.0 g methylhydroquinone 0.18 g 5-methylbenzotriazole 3.0 g sodium sulfite (anhydrous) 0.2 g benzyl alcohol 1.5 cc carboxymethylcellulose Na salt 58g Carbon black 150g Potassium hydroxide (28% aqueous solution) 200cc Water 680cc

The photosensitive elements 101, 201 to 206 are
After exposure from the emulsion layer side through a continuous gray wedge, the emulsion was superposed on the cover sheet, and the processing solution was spread between both materials using a pressure roller so that the thickness was 75 μm. The exposure was performed by adjusting the exposure illuminance so that the exposure amount was constant and exposed between 1/100 "and 10-4".
The treatment was carried out at 25 ° C., and after 10 minutes, the transfer density was measured with a color densitometer. The results are shown in Table-5. The maximum density, minimum density, reversal sensitivity and negative sensitivity shown in the table were determined as follows. That is, the horizontal axis shows the logarithm of the exposure amount and the vertical axis shows each color density, and a characteristic curve is drawn. The color density in the unexposed area was defined as the maximum density, and the color density in the area where the exposure amount was sufficiently large was defined as the minimum density. The sensitivity which gives an intermediate density between the maximum density and the minimum density in 1/100 "exposure was defined as the midpoint sensitivity, and the sensitivity which gave a density of the minimum density +1.0 in 10-4" exposure was defined as the negative sensitivity.

[0116]

[Table 10]

In the sample 203 of the present invention, the high negative sensitivity, which was a problem in the sample 201, was improved without impairing the high sensitivity of the midpoint sensitivity. It can be seen that the sensitivity has decreased.
Further, sample 202 and sample 205, sample 203 and sample 20
From the comparison of 6, the effects of the compounds of the general formulas [A], [B] and [C] of the present invention can be seen.

Example-2 In the same manner as in preparing the comparative photosensitive element (Sample 101), Example-1 Sample No. 1 of JP-A-2-90145.
The fourth, seventh, and twelfth emulsions of
Substituting the emulsions used in layers, 15th and 22nd layers,
Similar experiments were conducted. The results were the same as in Example-1, and the effect of the present invention was confirmed.

Example-3 A sample of Example-1 of JP-A-3-189643 was prepared in the same manner as in the preparation of a comparative photosensitive element (Sample 101).
The same experiment was carried out by substituting the emulsions of No. 106 third, fifth and ninth layers with the emulsions used in the eighth, fifteenth and twenty-second layers of the present invention. The results were the same as in Example-1, and the effect of the present invention was confirmed. Example-4 A method in which the samples 101 to 206 prepared in Example-1 were processed into a form that can be loaded into an instant camera and then photographed using the camera according to the procedure of Japanese Utility Model Publication No. Sho 63-150939. Then, the same experiment as in Example-1 was performed. The results were the same as in Example-1, and the effect of the present invention was confirmed.

[0120]

According to the present invention, it has been found that a tabular internal latent image type direct positive silver halide emulsion having high sensitivity and low re-reversal negative sensitivity, and a color diffusion transfer light-sensitive material using the same can be obtained.

[Brief description of drawings]

Figure 1: Thickness of emulsion outer shell

[Explanation of symbols]

 a is the thickness in the main plane direction b is the thickness in the direction perpendicular to the main plane

Claims (6)

[Claims] 1. An average grain diameter of 0.3 μm or more and an aspect ratio (diameter equivalent to circle of silver halide grain / grain thickness) of 2.
In an internal latent image type direct positive silver halide emulsion characterized by containing tabular silver halide grains of 100 or less and 50% or more of all silver halide grains, an average grain thickness a in the main plane direction of the outer shell Is 0.2 μm or more and 1.5 μm or less, and the average grain thickness b in the direction perpendicular to the main plane of the outer shell is 0.04 μm or more and 0.30 μm or less. Silver halide emulsion. 2. The internal latent image type direct positive silver halide emulsion according to claim 1, wherein the average grain thickness a of the outer shell in the main plane direction is 0.4 μm or more and 1.0 μm or less, and the outer shell main The average grain thickness b in the direction perpendicular to the plane is 0.
An internal latent image type direct positive silver halide emulsion characterized by having a size of from 06 μm to 0.15 μm. 3. The internal latent image type direct positive halogenated emulsion according to claim 1, wherein the coefficient of variation of grain thickness is 30% or more and the uniformity is high. Silver emulsion. 4. The internal latent image type direct positive silver halide emulsion according to claim 1, wherein at least one compound selected from the compounds represented by the following general formulas [A], [B] and [C] is present. An internal latent image type direct positive silver halide emulsion characterized in that an outer shell silver halide phase is formed below. [Chemical 1] In the formula, R, R ₁ and R ₂ may be the same or different,
It represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compound represented by the general formula [A], [B], or [C] is a polymer containing a divalent group derived from the structure represented by [A], [B], or [C] as a repeating unit. May be. If possible, R,
R ₁ , R _{2 and} L may be connected to each other to form a ring. 5. A silver halide color light-sensitive material containing at least one internal latent image type direct positive silver halide emulsion according to claim 3. 6. A silver developer having on a support at least one light-sensitive silver halide emulsion layer in combination with a dye image-forming substance, said dye image-forming substance being represented by the following general formula [I]. A non-diffusible compound releasing a diffusible dye or a precursor thereof in relation to, or a color diffusion transfer photosensitive material comprising a compound whose diffusivity of itself is changed,
2. At least one layer of said silver halide emulsion comprises:
A color diffusion transfer light-sensitive material comprising at least one internal latent image type direct positive silver halide emulsion described in 2 or 3. General formula [I] (DYE-Y) n-Z {DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like structure. To produce a difference in the diffusivity of the compound represented by (DYE-Y) n-Z corresponding to or opposite to the photosensitive silver salt having a latent image, or to release DYE and release DYE and ( DYE-Y) n -Z represents a group having a property of causing a difference in diffusibility,
n represents 1 or 2, and when n is 2, two DYE-
Y may be the same or different. }