JP2002006440A - Flat platy internal latent image type direct positive silver halide emulsion and color diffusion transfer photosensitive material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an internal latent image type direct positive silver halide emulsion giving a positive image having high sensitivity and a re-reversal negative image having low sensitivity and nearly free of desensitization in storage and to provide a color diffusion transfer photographic film unit (photosensitive material) using the emulsion. SOLUTION: In the internal latent image type direct positive silver halide emulsion containing flat platy silver halide grains having an average aspect ratio of >=8 formed through a step for forming core grains, a step for chemically sensitizing the core grains and a step for coating each of the core grains with a shell, the core grains are flat platy grains having an average aspect ratio of >=8. The color diffusion transfer photosensitive material contains the silver halide emulsion in at least one of silver halide emulsion layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a tabular internal latent image type direct positive silver halide photographic emulsion and a color diffusion transfer photosensitive material using the same.

[0002]

2. Description of the Related Art Photographs using silver halide have excellent sensitivity and gradation characteristics as compared with electrophotography or photographs obtained by combining various types of printers with a digital still camera in recent years, and are still widely used. In this,
A method for directly forming a positive image is known. this is,
For example, U.S. Pat.
As taught in U.S. Pat. No. 5,581,821, an internal latent image type direct positive silver halide photographic emulsion was used, and a silver halide grain having an internal latent image formed thereon was treated with a surface developer (a latent image forming site inside the silver halide grain). When developing with a developing solution that leaves substantially no development, a positive image is obtained by giving uniform exposure or using a nucleating agent. Some color photographic light-sensitive materials using the above-described internal latent image type direct positive silver halide photographic emulsion have been put to practical use, but when used for general-purpose color photographic photography, higher sensitivity has been desired.

In general, in order to increase the sensitivity of silver halide photographic emulsions, it is necessary to increase the surface area per grain by making the shape of the grains tabular and to adsorb a large amount of dye per grain to improve the light absorption efficiency. Done. A similar technique is effective for increasing the sensitivity of a positive image of an internal latent image type direct positive silver halide photographic emulsion. For example, JP-A-1-29764
No. 9, No. 6-51423, No. 7-333377, and No. 7-333767. In particular, JP-A-7-337377 discloses an emulsion having a high positive sensitivity and a low reversal negative image sensitivity by limiting the thickness of a shell in a direction perpendicular to the main plane in a tabular internal latent image type direct positive silver halide emulsion. Is obtained. Among them, examples of tabular grains having an aspect ratio of 7 are shown. However, tabular grains having an aspect ratio of more than 8 are generally described in the text, but no examples are given. However, higher sensitivity is required for the positive sensitivity. We have further increased the sensitivity by increasing the aspect ratio of the tabular grains to 8 or more. As a result, the sensitivity of the reinverted negative image (hereinafter referred to as "high illuminance negative sensitivity") which appears upon exposure to high illuminance at the same time as the sensitivity of the positive image (hereinafter referred to as "positive sensitivity") increases, and during storage, There is a problem that the sensitivity is lowered, which is an obstacle to practical use.

It has been shown in US Pat. No. 2,448,06 that silver halide emulsions can be sensitized by the addition of transition metal compounds at several stages in the manufacture of silver halide emulsions.
No. 0. It is known that there is a remarkable difference in the photographic effect of a transition metal compound in a silver halide emulsion between the case where a transition metal compound is added during silver halide grain formation and the case where it is added after silver halide grain precipitation. I have. The former case is particularly called a metal dopant. These are described in Research Disclosure, Volume 176, January 1978.
Published in February, Item 17643.

In an internal latent image type direct positive silver halide emulsion, it is known that doping with a metal ion hardens a low density portion on an inversion characteristic curve and increases sensitivity. For example, U.S. Pat. No. 3,271,157
Nos. 3,367,778 and 3,447,927
Nos. 3,531,291 and 3,761,267
Nos. 3,761,276 and 3,850,637
Nos. 3,923,513 and 4,035,185
Nos. 4,444,874 and 4,444,865
Nos. 4,433,047 and 4,395,478
No. 1,151,782, 1,529,0
No. 11, etc. However, hardening of the low concentration portion by doping with metal ions has not been sufficiently satisfactory. On the other hand, European Patent 0,336,
Nos. 425 and 0,336,426, JP-A-2-208
Nos. 53 and 2-20854 have excellent sensitivity and gradation stability over time in the presence of a six-coordinate rhenium, ruthenium, osmium and iridium metal complex having at least four cyano ligands, and have low sensitivity. A silver halide emulsion with improved illuminance failure is described, but no internal latent image type direct positive emulsion is described. Also,
JP-A-2-259,749, U.S. Pat.
No. 732 discloses a direct positive silver halide having a high maximum density and a low minimum density and a low re-reversal negative image at high illuminance exposure, particularly by an internal latent image type direct positive silver halide emulsion containing 6 cyano complexes among iron complexes. Although it is described that a silver halide emulsion can be obtained, there is no description about tabular grains having a high aspect ratio as in the present invention. JP-A-6-51423 discloses an internal latent image type direct positive silver halide emulsion containing a 6-cyano complex. Here, it is described that in the examples, when the central metal of the 6 cyano complex is iridium, cobalt, or ruthenium, it has the effect of increasing the midpoint sensitivity, increasing the sensitivity in the low-concentration part, and increasing the contrast as compared with the case of iron. However, there is no description about tabular grains. JP-A-7-333,767 discloses a tabular internal latent image type direct positive internal latent image type silver halide emulsion containing core grains and lead in a shell portion. Here, it is described that a direct positive silver halide emulsion having high sensitivity and excellent storage stability can be obtained. In our study, it was necessary to improve the sensitivity of positive images and the appearance of high-illumination negative images. As described above, several studies have been made with the aim of increasing the sensitivity of the positive image of the internal latent image type direct positive silver halide photographic emulsion and reducing the sensitivity of the reversal negative image. Was at a level where further improvement was desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high sensitivity positive image and a low reversal negative image sensitivity.
Another object of the present invention is to provide an internal latent image type direct positive silver halide emulsion with little desensitization during storage and a color diffusion transfer photographic film unit (light-sensitive material) using the same.

[0007]

The inventors of the present invention have conducted various studies to overcome the above-mentioned drawbacks of the conventional tabular internal latent image type direct positive silver halide emulsion. The present inventors have found that the aspect ratio of core grains in tabular grains, which has not been recognized in the internal latent image type direct positive silver halide emulsion, is an important factor. The present invention has been achieved by the following internal latent image type direct positive silver halide emulsion and a color diffusion transfer photographic material using the same. (1) The average aspect ratio of tabular silver halide grains is 8
The internal latent image type direct positive halogenation is formed by sequentially forming the tabular silver halide grains into a core grain, a step of chemically sensitizing the core grain, and a step of coating with a shell. An internal latent image type direct positive silver halide emulsion, wherein the core grains are tabular grains having an average aspect ratio of 8 or more. (2) adding at least one of the metal complexes represented by the following general formula (I) as a localized layer to a region of 0 to 60% of the silver amount used in the step of coating with the shell. The tabular internal latent image type direct positive silver halide emulsion according to item (1). General formula (I) [M (CN) _6-a L _a ] ^{n- wherein} M: Fe, Ru, Ir, Co, Cr, Mn, R
h, Re, Osa: 0, 1, or 2 L: Ligands other than CN n: 2, 3, or 4 Here, “0 to 60% of the amount of silver used in the coating step” "60%" indicates the ratio of the amount of silver used for shelling, and the region is any one of the timing of silver salt addition from the start of silver salt addition (0%) to the addition of 60% of silver for shelling. That point in time. That is, “0%” means the beginning of the addition of the silver salt, which corresponds to the case where the metal complex represented by the general formula (I) is added simultaneously with the silver salt. (3) having at least one light-sensitive silver halide emulsion layer combined with a dye-forming substance on a support, wherein the dye-forming substance is represented by the following general formula (II): In a color diffusion transfer photosensitive material that is a non-diffusible compound that releases a diffusible dye or a precursor thereof, or a compound that changes its own diffusivity, at least one of the silver halide emulsion layers is (1) or (2) A color diffusion transfer photosensitive material comprising the tabular internal latent image type direct positive silver halide emulsion as described in any of (2) above. General formula (II) (DYE-Y) _n -Z ｛DYE represents a dye group, a temporarily shortened dye or dye precursor group, Y represents a simple bond or a linking group, and Z represents a silver developing compound. Relatedly, it represents a group having a property of releasing a diffusible dye or a precursor thereof, or a group having a property of causing a difference in diffusivity of a compound represented by (DYE-Y) _n -Z, wherein n is 1 or 2 and when n is 2, the two DYE-Ys may be the same or different. ｝

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the general formula (I), M is preferably Fe and Ir, and most preferably Fe. Specific examples of the ligand other than CN represented by L in the general formula (I) include F, Cl,
Br, N ₃ , OCN, SCN, H ₂ O and the like.
Specific examples of the metal complex having at least four cyanogen ligands used in the present invention are shown below. [Fe (CN) _6] ^3- [Fe (CN) ₅ F] ^3- [Fe (CN) ₄ F _2] ^3- [Fe (CN) ₅ Cl] ^3- [Fe (CN) ₄ Cl _2] ^{3 -} [Fe (CN) ₅ Br] ^3- [Fe (CN) ₄ Br _2] ^3- [Fe (CN) ₅ (OCN)] ^3- [Fe (CN) ₅ (SCN)] ^3- [Fe (CN ) ₅ (N _3)] ^3- _{[Fe (CN) 5 (H 2} O) ] ^2- [Fe (CN) _6] ^4- [Fe (CN) ₅ F] ^4- [Fe (CN) ₄ F ₂ ] ^4- [Fe (CN) ₅ Cl] ^4- [Fe (CN) ₅ Cl _2] ^4- [Fe (CN) ₅ Br] ^4- [Fe (CN) ₄ Br _2] ^4- [Fe (CN) ₅ (OCN)] ^4- [Fe (CN) ₅ (SCN)] ^4- _{[Fe (CN) 5 (N 3} ) ] ^4- _{[Fe (CN) 5 (H 2} O) ] ^3-

As counter ions of these metal complexes, ammonium and alkali metal ions such as sodium and potassium are preferably used. The content of the metal complex having at least four cyanogen ligands used in the present invention is preferably at least 1.0 × 10 ⁻⁷ mol and less than 1.0 × 10 ⁻⁴ mol per mol of silver halide. More preferably, the amount is 1.0 × 10 ⁻⁵ mol or more and 5 × 10 ⁻⁴ mol or less per mol of silver halide. These metal complexes are dissolved in water or other suitable solvent and added directly to the reaction solution when forming silver halide grains, or in an aqueous halide solution for forming silver halide grains, or in an aqueous silver salt solution. It is preferable to add it to the solution by adding it to a medium or other solution to form particles. Further, it is also preferable to add and dissolve silver halide fine particles containing a metal complex in advance and to deposit on a separate silver halide particle to contain these metal complexes. The expression “in a dispersion medium containing at least one metal complex represented by the general formula (I)” described in the specification of the present application is used in a sense including the above-described embodiment. The pH of the hydrogen ion concentration in the reaction solution when these metal complexes are added is preferably 1 or more and 10 or less, more preferably 3 or more and 7 or less. The metal complex represented by the general formula (I) may be present at any point during the formation of the particles, and may be present during the formation of the core and / or the shell, but at least during the formation of the shell. It is preferred that The pBr during particle formation when these metal complexes are added is preferably 2 to 4 at 75 ° C, more preferably 2.42 to 3.29. The six-coordinate iron complex used in the present invention can be used in combination with other metal ions. Mg, Ca, Sr, B as other metals
a, Al, Sc, Y, La, Cr, Mn, Ni, Cu,
Zn, Ga, Ru, Rh, Pd, Re, Os, Pt, A
u, Cd, Hg, Tl, In, Sn, Pb, Bi and the like can be used. These metals are ammonium salts,
A salt, such as an acetate, a nitrate, a sulfate, a phosphate, a hydroxide, a six-coordinate complex, or a four-coordinate complex, can be added as long as it can be dissolved at the time of particle formation. Further, an iron complex other than the metal complex represented by the general formula (I) may be used in combination.

The internal latent image type direct positive silver halide emulsion (hereinafter sometimes abbreviated as "internal latent image type silver halide emulsion") of the present invention is mainly composed of an internal latent image type silver halide emulsion when exposed to light. Specifically, a silver halide emulsion which forms a latent image on a transparent support is coated with a predetermined amount of the silver halide emulsion, and is exposed for a fixed time of 0.01 to 1 second. In the following developer A ("internal type" developer), a second sample exposed in the same manner as described above and having a maximum density obtained when developed at 20 ° C. for 5 minutes was subjected to the following developer B (“surface (Developer) at 20 ° C. for 5 minutes. Here, the maximum density is measured by an ordinary photographic density measurement method. Developer A N-methyl-p-aminophenol sulfite 2 g Sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g Potassium bromide 5 g Potassium iodide 0.5 g B N-methyl-p-aminophenol sulfite 2.5 g L-ascorbic acid 10 g Potassium metanitrate 35 g Potassium bromide 1 g Add water and add 1 liter

As the internal latent image type silver halide emulsion, for example, US Pat. No. 2,456,953 and US Pat.
Conversion-type silver halide emulsion described in U.S. Pat. No. 2,935,014, and the like.
And silver halide emulsions in which the halogen composition of the first phase and the second phase are different from each other as described in JP-A No. / Shell type silver halide emulsion. Of these, a core / shell type silver halide emulsion is particularly preferred as the internal latent image type silver halide emulsion used in the present invention.
No.13, No.3,317,322, No.3,761,26
No. 6, No. 3, 761, 276, No. 3, 850, 637
Nos. 3,923,513 and 4,035,185
Nos. 4,184,878 and 4,395,478
No. 4,504,570, JP-A-57-13664.
No. 1, No. 61-3137, and JP-A No. 61-299155.
And JP-A-62-208241.

In order to obtain a direct positive image, a uniform second exposure is applied to the front surface of the exposed layer after the above-described internal latent image type silver halide emulsion has been image-exposed and before or during development processing (see “Light Fogging method ", for example, British Patent No. 1,151,36
No. 3) or a development treatment in the presence of a nucleating agent ("Chemical fogging method", for example, Research Disclosure, Vol. 151, No. 15162,
76 to 78), but in the present invention,
A method of directly obtaining a positive image by the "chemical fogging method" is preferred. 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, a uniform second exposure is applied to the entire surface after image exposure, before development processing or during development processing, or It can be obtained by performing development processing in the presence of a nucleating agent. As the nucleating agent, US Pat. No. 2,563,
Nos. 785 and 2,588,982; hydrazides and hydrazones described in U.S. Pat. No. 3,227,552; British Patent 1,283,
No. 835, JP-A-52-69613, and JP-A-55-138.
No. 742, No. 60-11837, No. 62-21045
No. 1, 62-291637, U.S. Pat.
5,515, 3,719,494 and 3,73
4,738, 4,094,683, 4,11
No. 5,122, No. 4,306,016, No. 4,47
Heterocyclic quaternary salt compounds described in U.S. Pat. No. 1,044, etc .; sensitizing dyes having a nucleation-forming substituent in a dye molecule described in U.S. Pat. No. 3,718,470; Nos. 4,030,925, 4,031,127, 4,245,037, 4,255,511, 4,266,013, 4,276,364 and British Patent Thiourea-bonded acylhydrazine-based compounds described in U.S. Pat.
80,270, 4,278,748, British Patent No. 2,011,391B, etc., and sialhydrazine-based compounds having a heterocyclic group such as a thioamide ring or a triazole or tetrazole bonded as an adsorbing group. Used. The amount of the nucleating agent used here is desirably an amount that gives a sufficient maximum density when the internal latent image type emulsion is developed with a surface developer. In practice, the appropriate content may vary over a wide range because it depends on the characteristics of the silver halide emulsion used, the chemical structure of the nucleating agent, and the development conditions. A range of about 0.1 mg to 5 g per mole is practically useful, preferably about 0.5 mg to 2 g per mole of silver. When it is contained in the hydrophilic colloid layer adjacent to the emulsion layer, the same amount as described above may be contained with respect to the amount of silver contained in the inner latent type emulsion having the same area.

The internal latent image type direct positive silver halide emulsion of the present invention contains tabular silver halide grains. Tabular silver halide grains are silver halide grains having two opposite parallel main planes and having an aspect ratio of 2 or more. The aspect ratio is defined as the circle equivalent diameter of two opposing parallel principal planes (the diameter of a circle having the same projected area as the principal plane) divided by the distance of the principal plane (grain thickness). The above tabular grains contained in the silver halide emulsion have an average aspect ratio of 8 or more. The circle-equivalent diameter Di and the particle thickness hi of the projected area of each particle can be easily obtained from observation with an electron microscope. The average aspect ratio is defined as a value obtained by dividing the average value of the circle equivalent diameter Di of each tabular grain by the average value of the grain thickness hi. The internal latent image type direct positive silver halide emulsion of the present invention is formed through a first step of forming core grains, a second step of chemically sensitizing the core grains, and a third step of coating with a shell. You. The core grains of the internal latent image type direct positive silver halide emulsion of the present invention have an average aspect ratio of 8 or more. The production method is not particularly limited, and examples thereof include JP-A-58-108525, JP-A-58-108526, and JP-A-62-157024.
JP-A-62-163046, JP-A-2-2229
No. 40, JP-A-2-193137, JP-A-2-838
No. etc. can be referred to. Further, Japanese Patent Application Laid-Open No. 63-1
Also preferred are grains having a grain thickness and a distance between twin planes described in No. 63451.

The halogen composition of the core grains of the internal latent image type direct positive silver halide emulsion of the present invention is not particularly limited.
Silver bromide or silver iodobromide comprising 95 mol% or more of silver bromide is preferred. The morphology of the core particles used in the present invention is preferably uniform among the particles. Monodispersity of sphere equivalent diameter di (= standard deviation of di / average value of di), particle thickness h
The monodispersity of i (= standard deviation of hi / average value of hi) is preferably 20% or less. The core particles used in the present invention preferably do not contain lattice defects such as screw dislocations and edge dislocations. The step of subjecting the core particles to chemical sensitization is performed by adding at least one kind of gold sensitizer and ripening. Other known sulfur sensitizers, oxidizing agents, and other chemical sensitizers can be used. As the oxidizing agent, the oxidizing agents described in JP-A-61-3134 and JP-A-61-3136 can be used. JP-A-2-
No. 191938, which is represented by the general formulas (I), (II), and (III), or JP-A No. 7-333782 describes a general formula [A].
It is preferable to use a thiosulfonic acid compound represented by [B] or [C] in combination. The step of subjecting the core particles to chemical sensitization is preferably performed by aging at a pH of 4.5 to 7.0 and a pAg of 8 to 10. The step of subjecting the core particles to chemical sensitization comprises the following general formula (III) during chemical ripening:
It is preferable to use a compound represented by

Formula (III) A- (W) _n -R In the formula (III), A represents an atom group containing a group capable of being adsorbed to silver halide, W represents a divalent linking group, n represents 0 or 1, and R represents a reducing group. In the general formula (III),
A is a mercapto compound (for example, a mercaptotetrazole group, a mercaptotriazole group, a mercaptoimidazole group, a mercaptothiadiazole group, a mercaptooxadiazole group, a mercaptobenzthiazole group, a mercaptobenzoxazole group, a mercaptobenzimidazole group, a mercaptotetrazole group, Azaindene group, mercaptopyridyl group, mercaptoalkyl group, mercaptophenyl group, etc., thione compound (for example, thiazoline-2-thione group, imidazoline-2-thione group, benzimidazoline-2-thione group, benzthiazoline-
Examples thereof include 2-thione group, thiourea group, thioamide group and the like, and compounds forming imino silver (for example, benzotriazole group, tetrazole group, hydroxytetraazaindene group, benzimidazole group and the like). Among them, mercapto compounds and thione compounds are preferred. General formula (II
In I), W represents a divalent linking group composed of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom and a sulfur atom, and specifically, an alkylene group having 1 to 20 carbon atoms (for example, methylene Group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, etc.), arylene group having 6 to 20 carbon atoms (eg, phenylene group, naphthylene group, etc.),-
CONR ^1- , -SO ₂ NR ^2- , -O-, -S-, -N
R ³ —, —NR ⁴ CO—, —NR ⁵ SO ₂ —, —NR ⁶ CO
NR ⁷ —, —COO—, —OCO— and the like. Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are an aliphatic group,
Or it represents an aromatic group. Two or more of these groups may be appropriately combined to form a divalent linking group.

The aliphatic group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ preferably has 1 to 30 carbon atoms, and particularly preferably has 1 to 30 carbon atoms. 20 linear, branched or cyclic alkyl, alkenyl, alkynyl and aralkyl groups. For example, methyl group, ethyl group, isopropyl group, t-butyl group, n-octyl group, n-decyl group, n
-Hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3
-Pentenyl, propargyl, 3-pentynyl,
And a benzyl group. R ¹ , R ² , R ³ , R ⁴ ,
The aromatic group represented by R ⁵ , R ⁶ and R ⁷ is preferably an aromatic group having 6 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 20 carbon atoms. Phenyl group,
And a naphthyl group. The precursor of the compound having an adsorbing group and a reducing group to silver halide, when added to a silver halide emulsion, undergoes a chemical reaction such as an oxidation-reduction reaction or a hydrolysis reaction to form the compound of the general formula (II). Release. For example, thiazolium salts (including benzothiazoliums and naphthothiazoliums), thiazolines, thiazolidines, and the like, which form a mercapto group as an adsorptive group and a formyl group as a reducing group by a hydrolysis reaction (for example, compound 13) And a disulfide compound having a reducing group in which a disulfide group is cleaved to generate a mercapto group as an adsorptive group. Specific examples of the compound represented by the general formula (III) are shown below.

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

The step of coating with a third shell is described in, for example, the embodiment of JP-A-63-151618, US Pat.
6,316, 3,317,322 and 3,76
Nos. 1,276, 4,269,927 and 3,36
7,778, JP-A-58-108525, JP-A-5-108525
8-108526, JP-A-62-157024, JP-A-62-163046, JP-A-2-222940
No., JP-A-2-193137, JP-A-2-838,
JP-A-7-337377 can be referred to. The grains after coating with the shell of the internal latent image type direct positive silver halide emulsion of the present invention have an average aspect ratio of 8 or more.
The particles after being coated with the shell used in the present invention preferably have a uniform form among the particles. Monodispersity of sphere equivalent diameter di (= standard deviation of di / average value of di), particle thickness hi
Is preferably not more than 20% in each case (= standard deviation of hi / average value of hi). The halogen composition of the shell of the internal latent image type direct positive silver halide emulsion of the present invention is not particularly limited, but silver iodobromide comprising 95 mol% or more of silver bromide is preferred. The halogen composition of the core particle and the shell may be different. The particles used in the present invention preferably do not contain lattice defects such as screw dislocations and edge dislocations. The volume ratio of the core particles to the shell is preferably in a molar ratio of core particles / shell = 1/20 to 1/1.

US Pat. Nos. 4,334,012, 4,301,241, and 4,150,994 apply a method in which silver halide grains which have been previously precipitated are added to a reaction vessel for preparing an emulsion. 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, and the addition method can be selected from the method of adding the whole amount at once, adding the emulsion in a plurality of times, or adding continuously. It is also effective in some cases to add particles having various halogen compositions to modify the surface.

In addition to the method of adding a soluble silver salt and a 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;
As described in JP-A-4,242,455, a particle forming method in which the concentration is changed or the flow rate is changed is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. If necessary, it is more preferable to reduce the amount of silver halide supplied. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is. A mixer for reacting a solution of a soluble silver salt with a soluble halide salt is disclosed in U.S. Pat. West German Patent Nos. 2,556,885 and 2,555,364.
Can be used by selecting from the methods described in the above item.

In the preparation of an emulsion containing tabular grains,
In order to accelerate grain growth, a silver salt solution (eg, Ag
It is preferable to increase the addition speed, amount and concentration of the NO ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution). Regarding these methods, for example, British Patent No. 1,335,925, US Pat. No. 3,672,90
No. 0, 3,650,757, 4,242,445
And JP-A-55-142329 and JP-A-55-15812.
No. 4, etc. can be referred to.

In some cases, a method of adding a chalcogenide compound during emulsion preparation as described in US Pat. No. 3,772,031 is effective. In addition to S, Se, Te, cyanide, thiocyanate, selenocyanate, carbonate,
Phosphates and acetates may be present. These are disclosed in U.S. Pat. Nos. 2,448,060 and 2,628,
167, 3,737,313, 3,772,0
No. 31, Research Disclosure, 134
Vol., June 1975, 13452, and the like.

The shape of the tabular grains contained in the silver halide emulsion of the present invention can be selected from triangles, hexagons, circles and the like. A regular hexagon having approximately equal six sides as described in U.S. Pat. No. 4,996,137 is a preferred form. In the present invention, the tabular grains are silver halide grains having an aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of 2 or more and 100 or less, and the tabular grains are all halides in the emulsion used in the present invention. 50 of silver particles
% (Area) or more. Preferably, the aspect ratio is 5
As described above, more preferably, silver halide grains having an aspect ratio of 5 or more and 8 or less account for 50% of all silver halide grains in the emulsion.
% (Area) or more, preferably 70% or more.
%, Particularly preferably 85% or more. Here, the equivalent circle diameter in tabular grains is the equivalent circle diameter of two opposing parallel or nearly parallel main planes (diameter of a circle having the same projected area as the main plane), and the grain thickness is the main equivalent diameter of the main plane. Represents the distance between planes. Also, if the aspect ratio is 1
If it exceeds 00, the emulsion is undesirably deformed or destroyed in the process until the emulsion is completed as a coated product.

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
It is 5.0 μm, and more preferably 0.5 to 3.0 μm. Tabular grain thickness is less than 1.5 μm, preferably 0.0
5 to 1.0 μm. Furthermore, the variation coefficient of the particle thickness is 3
Emulsions having a thickness uniformity of 0% or less are also preferred. Further, the grains described in JP-A-63-163451, in which the thickness of grains and the distance between twin planes are specified, are also preferable. The measurement of the grain diameter and grain thickness of tabular grains is described in US Pat.
It can be determined by an electron micrograph of the particles as in the method described in JP-A-34,226.

The particle size distribution of the tabular grains is arbitrary, but preferably monodispersed. Here, the monodispersion means that 95% of the total mass or the total number of silver halide grains contained therein is within ± 60% of the number average grain size,
It is preferably defined as a dispersion that falls within 40% of the size. Here, the number average grain size is the number average diameter of the projected area diameter of the silver halide grains. The structure and production method of monodisperse tabular grains are described, for example, in JP-A-63-151618, and these monodisperse emulsions may be used as a mixture.

As the silver halide composition of these grains, any of silver iodobromide, silver iodochlorobromide and silver chloroiodide may be used, but silver iodobromide is preferred.

The silver halide grains have different phases between the inside and the surface. The silver halide composition inside the grains may be uniform or may be composed of a heterogeneous silver halide composition. The surface phase may be a discontinuous layer or may have a continuous layer structure. Further, particles having dislocation lines may be used.

It is important to control the halogen composition in the vicinity of the surface of the grain. When the halogen composition in the vicinity of the surface is changed, either a structure that covers the entire grain or a structure in which only a part of the grain is attached can be selected. . For example, this is a case where the halogen composition is changed only on one side of the tetradecahedral grain composed of the (100) plane and the (111) plane, or the halogen composition on one of the main plane or the side face of the tabular grain is changed.

It is possible to use two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions, etc., and to use them 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 to coat the shell on the chemically sensitized core grain and then further sensitize the grain surface, since the maximum density is high and good reversal performance is exhibited. . When chemical sensitization is performed on the grain surface, a polymer as described in JP-A-57-13641 may be allowed to coexist. The chemical sensitization was performed by James, Theory of the Photographic
Process, 4th edition, published by Macmillan, 1977, (T.
H. James, The Theory of the Photographic Process,
4th ed., Macmillan, 1977), using active gelatin as described on pages 67-76;
Research Disclosure, Volume 120, 1974
April 2008, Research Disclosure,
34, June 1975, 13452, U.S. Pat.
No. 642,361, No. 3,297,446, No. 3,7
Nos. 72,031, 3,857,711, 3,90
Nos. 1,714, 4,266,018, and 3,9
04,415 and British Patent 1,315,755.
At a pAg of 5 to 10, pH of 4 to 8 and a temperature of 30 to 80 ° C., sulfur, selenium, tellurium, gold,
It can be performed using platinum, palladium, iridium, rhodium, osmium, rhenium, or a combination of a plurality of these sensitizers.

The chemical sensitization in the photographic emulsion of the present invention is F
Although it can be carried out with a metal material such as e, Cr, Mn, Ni, Mo, Ti, etc., it is more preferred to carry out the treatment in a nonmetallic material whose metal surface is coated with a fluororesin. Examples of the fluororesin material include Teflon (registered trademark) coating materials PFA, TFE, and FEP developed by DuPont.

Chemical sensitization can be carried out in the presence of a chemical sensitization auxiliary. Compounds known to suppress fog and increase sensitivity in the course of chemical sensitization, such as azaindene, azapyridazine and azapyrimidine, are used as the chemical sensitization aid. Examples of chemical sensitizers are
U.S. Pat. Nos. 2,131,038 and 3,411,91
Nos. 4,554,757, JP-A-58-1265.
No. 36, No. 62-253159, and in "Photographic Emulsion Chemistry" by Duffin, pp. 138-143 (Focal Press, 1966).

Japanese Patent Publication No. 58-1410, Moiser
ar) et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27. Silver halide emulsions can reduce and sensitize the interior of grains during precipitation. . The following reduction sensitization can also be used as chemical sensitization. US Patent 3,891,
No. 446 and 3,984,249, for example, reduction sensitization can be performed using hydrogen,
U.S. Pat. Nos. 2,518,698 and 2,743,18
No. 2 and U.S. Pat. No. 2,743,183, using a reducing agent or low pAg (eg, less than 5) or high pAg.
Reduction sensitization can be achieved by H (for example, greater than 8) treatment. As typical reduction sensitizers, stannous salts, ascorbic acid and derivatives thereof, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. The chemical sensitization method described in U.S. Pat. Nos. 3,917,485 and 3,966,476 can also be applied.

Japanese Patent Application Laid-Open Nos. 61-3134 and 61-3
The sensitization method using an oxidizing agent described in JP-A-136 can also be applied. The oxidizing agent for silver refers to a compound having an action of converting metallic silver into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, and silver selenide, or may form a silver salt that is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be inorganic or organic. As the inorganic oxidizing agent, ozone, hydrogen peroxide and its adducts (for example, Na
BO ₂ · H ₂ O ₂ · 3H ₂ O · 2NaCO ₃ · 3H ₂ O ₂ , N
_{a 4 P 2 O 7 · 2H} 2 O 2, 2Na 2 SO 4 · H 2 O 2 · 2H
₂ O), peroxy acid salts (eg, K ₂ S ₂ O ₈ , K ₂ C)
₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compounds (for example,
K _{2 [Ti (O 2) C 2 O} 4 ] _{· 3H 2 O, 4K 2 SO} 4 · T
i (O ₂ ) OH.SO ₄ .2H ₂ O, permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr)
Oxygenates such as ₂ O ₇ ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), and salts of high-valent metals (eg, potassium hexacyanoferric acid) are given. is there. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B). ) Is given as an example. Preferred oxidizing agents of the present invention are organic oxidizing agents such as ozone, hydrogen peroxide and its adducts, halogen elements and quinones. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a reverse method, or a method of coexisting both methods. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

As a dispersion medium (protective colloid) used for preparing the emulsion of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl Alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Photo.Japa
n, No. 16, P30 (1966), and an enzyme-treated gelatin may be used, and a hydrolyzate or an enzyme-decomposed product of gelatin may also be used. Gelatin contains many impurity ions, but it is also preferable to use gelatin in which the amount of inorganic impurity ions has been reduced by ion exchange treatment.

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

In the present invention, spectral sensitization can be performed using a sensitizing dye. The sensitizing dyes used include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. More specifically, U.S. Pat.
No. 61-160739, RD17029 (1978)
Year) p. 12-13, RD17643 (1978) 23
And the like, sensitizing dyes described on pages, and the like.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,9.
77,229, 3,397,060, 3,52
2,052, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377, 3,76
9,301, 3,814,609, 3,83
Nos. 7,862, 4,026,707, British Patent Nos. 1,344,281, 1,507,803, JP-B-43-4936, JP-B-53-12375, and JP-A-5
Nos. 2-110618 and 52-109925.

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. (For example, U.S. Pat. Nos. 3,615,613, 3,
No. 615,641, No. 3,617,295, No. 3,6
No. 35,721, No. 2,933,390, No. 3,74
3,510 and JP-A-63-23145). The sensitizing dye for spectral sensitization may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, it is performed after completion of chemical sensitization and before coating, but US Pat.
As described in JP-A Nos. 628,969 and 4,225,666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before completion of precipitation of silver halide grains to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder may be chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains have been formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756. In order to achieve the object of the present invention, the addition is preferably performed during the chemical sensitization step of the shell portion, and particularly preferably added near the end of the chemical sensitization.

The sensitizing dye may be used in an amount of from 10 ^-8 to 10 ^-2 mol per mol of silver halide, and a more preferable silver halide grain size is from 0.2 to 1.2 μm.
In this case, about 5 × 10 ⁻⁵ to 2 × 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 a reduction in sensitivity and the occurrence of fog. For example, RD17643
(1978) 24-25, U.S. Patent No. 4,629,
No. 678, azoles and azaindenes described in JP-A-59-168442, or nitrogen-containing carboxylic acids and phosphoric acids, or mercapto compounds and metal salts thereof described in JP-A-59-111636, -87
No. 957, acetylene compounds and the like are used. Also, phenethyl alcohol and JP-A-63-25
Nos. 7747 and 62-272248, and
1,2-benzisothiazoline described in No. 80941
3-one, n-butyl, P-hydroxybenzoate,
It is preferable to add various preservatives or fungicides such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. See European Patent No. 4
36, 938A2, page 150, lines 25-28. These additives are described in more detail in Research Disclosure Item 17643 (1978),
Item 18716 (November 1979) and Item 30
7105 (November 1989), and the relevant locations are summarized in the table below.

Type of Additive RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1989) 1 Chemical sensitizer page 23 648 right column page 866 2 Sensitivity enhancer 648 page right column 3 Spectral sensitizer, page 23-24 page 648 right column 866-868 Super sensitizer ~ page 649 right column 4 Brightener 24 page 647 page 868 5 Fog prevention 24-25 page 649 right column 868- Page 870 Agents, stabilizers 6 Light absorbers, pages 25-26, page 649, right column, page 873, filters-page 650, left column Dyes, ultraviolet absorbers 7 Stain, page 25, right column, page 650, left column, page 872 Inhibitors, right column 8 Dye image 25 pages 650 left column 872 Stabilizer 9 Hardener 26 pages 651 left column 874-875 10 Binder page 26 Same as above 873-874 11 Plasticizer 27 page 650 right column page 876 Lubrication Agent 12 Coating aid, pages 26-27 Same as above, pages 875-876 Surfactant 13 Static page 27 Same as above, pages 876-877 Inhibitor 14 Matting agent 878-879

The internal latent image type direct positive silver halide emulsion of the present invention can be used for conventional light-sensitive materials, but is preferably used for color diffusion transfer light-sensitive materials. Next, the color diffusion transfer photosensitive material of the present invention will be described. The most typical form of the color diffusion transfer material is a color diffusion transfer film unit, and the typical form is such that the image receiving element and the photosensitive element are laminated on one transparent support, and the transferred image is formed. After completion of the above, there is no need to peel the photosensitive element from the image receiving element. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye image-forming compound in each of the above emulsion layers; A magenta dye image-forming compound and a cyan dye image-forming compound are each combined (herein, the term “infrared-sensitive emulsion layer” means an emulsion having a spectral sensitivity maximum with respect to light of 700 nm or more, particularly 740 nm or more. Layer). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the dye image forming compound-containing layer so that the transferred image can be viewed through the transparent support.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the developing process can be completed in a bright place. If desired, a release layer may be provided at an appropriate position so that all or a part of the photosensitive element can be peeled from the image receiving element. Such an embodiment is disclosed in, for example,
67840 and Canadian Patent 674,082.

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

In another embodiment which does not require peeling, the above-described photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. .
An image receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support, and an embodiment in which the photosensitive element is intentionally peeled from the image receiving element is described in US Pat. No. 3,730,7.
No.18.

On the other hand, there are roughly two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports, respectively, one of which is a peeling type, and the other is a peeling-free type. is there. More specifically, in a preferred embodiment of the peelable film unit, at least one image receiving layer is coated on one support, and the photosensitive element is coated on a support having a light shielding layer. Before the end of the exposure, the coated surface of the photosensitive layer and the coated surface of the mordant layer do not face each other, but after the end of the exposure (for example, during the developing process), the coated surface of the photosensitive layer is inverted in the image forming apparatus and comes into contact with the coated surface of the image receiving layer. It is devised as follows. After the transfer image is completed in the mordant layer, the photosensitive element is immediately separated from the image receiving element. In a preferred embodiment of the peeling-free film unit, at least one mordant layer is applied on a transparent support, and the photosensitive element is applied on a support having a transparent or light-shielding layer, The photosensitive layer application surface and the mordant layer application surface face each other and are superimposed.

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

The 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 a substance which changes its own diffusivity. And the 4th of The Theory of the Photographic Process
It is stated in the edition. All of these compounds can be represented by the following general formula (II). Formula (II) (DYE-Y) _n -Z ｛DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group,
Z is related to silver development (specifically, corresponding to or inversely corresponding to a photosensitive silver salt having an image-like latent image) (DYE-Y)
causing a difference in the diffusivity of the compound represented by _n- Z,
Or a group having the property of releasing DYE (diffusible dye or its precursor) and causing a difference in diffusivity between the released DYE and (DYE-Y) _n -Z, Represents 1 or 2, and when n is 2, two DYEs
-Y may be the same or different.機能 Due to the function of Z, the compound is roughly classified into a negative type compound which becomes diffusible in a silver developed portion and a positive type compound which becomes diffusible in an undeveloped portion. Specific examples of the negative type Z include those which oxidize as a result of development and are cleaved to release a diffusible dye.
Specific examples of Z are described in U.S. Pat.
Nos. 993,638, 4,076,529 and 4,1
No. 52,153, No. 4,055,428, No. 4,05
No. 3,312, No. 4,198,235, No. 4,17
9,291, 4,149,892 and 3,84
4,785, 3,443,943, 3,75
No. 1,406, No. 3,443,939, No. 3,44
No. 3,940, No. 3,628,952, No. 3,98
0,479, 4,183,753, 4,14
Nos. 2,891, 4,278,750, 4,13
9,379, 4,218,368, 3,42
1,964, 4,199,355, 4,19
9,354, 4,135,929, 4,33
6,322,4,139,389,
No. 50736, No. 51-104343, No. 54-13
No. 0122, No. 53-110827, No. 56-126
No. 42, No. 56-16131, No. 57-4043,
No. 57-650, No. 57-20735, No. 53-6
Nos. 9033, 54-130927, 56-164
342, 57-119345 and the like. Among the Z of the negative dye releasing redox compound, a particularly preferred group is an N-substituted sulfamoyl group (N-
Examples of the substituent include a group derived from an aromatic hydrocarbon ring or a hetero ring). The representative groups of Z are exemplified below, but are not limited thereto.

[0053]

Embedded image

For compounds of the positive type, see Angev. Chem. Int. Ed. Engl., 22, 191.
(1982). As a specific example, a compound (dye developing agent) which is initially diffusible under alkaline conditions, but is oxidized by development to become non-diffusible is exemplified. Effective Z for compounds of this type is described in US Pat.
No. 83606 is representative. Also,
Another type is a type which releases a diffusible dye by, for example, self-ring closure under alkaline conditions, but substantially does not release the dye when oxidized during development. Specific examples of Z having such a function are described in U.S. Pat. No. 3,980,479, JP-A-53-69033, and JP-A-54-130927, and U.S. Pat.
No. 4,199,355 and the like. Another type does not release the dye itself, but releases the dye when reduced. Compounds of this type can be used in combination with an electron donor to release the diffusible dye imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. For an atomic group having such a function, see, for example, US Pat.
No. 3,753, No. 4,142,891, No. 4,27
8,750, 4,139,379, 4,21
No. 8,368, JP-A-53-110827, U.S. Pat. Nos. 4,278,750, 4,356,249, 4,358,535, JP-A-53-110827,
JP-A-54-130927, JP-A-56-164342, Published Technical Report 87-6199, European Patent Publication 220746A
No. 2, etc. Specific examples of Z will be described below, but the present invention is not limited thereto.

[0055]

Embedded image

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

[0057]

Embedded image

The details are described in US Pat. No. 3,719,489.
And No. 4,098,783. on the other hand,
Specific examples of the dye represented by DYE in the above general formula are described in the following documents. Examples of yellow dyes: US Pat. No. 3,597,200,
3,309,199, 4,013,633, 4,245,028, 4,156,609, 4,139,383, 4,195,992, and 4 Nos. 4,148,643, 4,336,322: JP-A-51-114930,
No. 56-71072: Research Disclosure 1763
No. 0 (1978) and No. 16475 (1977). Examples of magenta dyes: U.S. Pat. No. 3,453,107;
3,544,545, 3,932,380, 3,931,144, 3,932,308, 3,954,476, 4,233,237, and 4 , 255,509, 4,250,246, 4,142,891, 4,207,104, 4,287,292: JP-A-52-106727,
Nos. 53-23628, 55-36804, 56
No. -73057, No. 56-71060, No. 55-13
What is described in No. 4. Examples of cyan dyes: U.S. Pat. Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220 and 4, Nos. 242,435, 4,142,891, 4,195,994, 4,147,544 and 4,148,642; British Patent 1,551,138
Nos .: JP-A-54-99431 and JP-A-52-8827,
Nos. 53-47823, 53-143323, 5
4-99431 and 56-71061; European Patents (EP) 53,037 and 53,040; Rese
Arch Disclosure 17,630 (1978) and 16,475 (1977). These compounds are described in JP-A-62-215272, 14
It can be dispersed by the method described on pages 4-146. These dispersions are described in JP-A-62-215,272.
No. 137-144 may be included.
Further, the internal latent image type direct positive silver halide emulsion of the present invention may be used for a conventional light-sensitive material. Applicable photosensitive materials include photosensitive materials for color and black-and-white printing paper, photosensitive materials for color slides, and photosensitive materials for microfilms.

[0059]

EXAMPLES Example 1 Preparation of Core Particle Emulsion (Step of Forming Core Particles) Preparation of CR-01 6 liters of H ₂ O, low molecular weight gelatin having an average molecular weight of 20,000 or less in a reaction vessel maintained at 35 ° C. 5 g and 4.4 g of potassium bromide were added and mixed with stirring. Then, 44.2
375 ml of an aqueous silver nitrate solution having a concentration of g / l and 412 ml of an aqueous solution containing 30.9 g / l of potassium bromide and 20 g / l of low molecular weight gelatin having an average molecular weight of 20,000 or less were added over 1 minute. After adding 2.6 g of potassium bromide, the temperature was raised to 75 ° C. with a gradient of 1.5 ° C. in one minute. Then 175g
Aqueous solution obtained by adding 1255 g of H ₂ O to deionized gelatin of
An aqueous solution containing 10.4 g of compound C-104 was added.
Subsequently, 23 ml of a 50% aqueous solution of ammonium nitrate and 120 ml of a 1 mol / l aqueous solution of sodium hydroxide were added, and after aging for 10 minutes, 9.5 ml of 100% acetic acid, 5.7 g of potassium bromide and 40 mg of compound C-101 were added. Subsequently, an aqueous silver nitrate solution having a concentration of 214 g / l and an aqueous potassium bromide solution having a concentration of 150 g / l were pAg7.
While maintaining the temperature at 5, the mixture was added by the double jet method. Silver nitrate was added in an amount of 51 g while being accelerated over 16 minutes so that the final speed was 1.7 times the initial speed. Subsequently, after adding 69 mg of compound C-105, 350
An aqueous silver nitrate solution having a concentration of g / l and an aqueous potassium bromide solution having a concentration of 245 g / l were double-jetted to a pAg of 7.5.
And added by the double jet method. Silver nitrate was added in an amount of 635 g while accelerating over 84 minutes such that the final speed was 2.6 times the initial speed. Subsequently, an aqueous solution obtained by adding 875 ml of H ₂ O to 120 g of deionized gelatin was added, and then an aqueous solution of silver nitrate having a concentration of 350 g / l and an aqueous solution of potassium bromide having a concentration of 245 g / l were double-jetted to a pAg of 7.5. The solution was kept and added by the double jet method. The amount by which the amount of silver nitrate added becomes 867 g is 64
Over a period of minutes, the addition was performed while accelerating so that the final speed was 1.5 times the initial speed.

After adding 68 g of potassium bromide, washing with water by the usual flocculation method, deionized gelatin and H ₂ O were added, and 1.62 mol per kg of emulsion was added.
Silver, 17.8 g gelatin. p
H was adjusted to 6.5 pAg to 9.3. The value of the diameter of a sphere having the same volume as each particle is called a sphere equivalent diameter, and the diameter of a circle having an area equal to the projected area of each particle as viewed from the main plane direction is called a circle equivalent diameter. Particles obtained as a result of observation with an electron microscope have an average value (= Σ) of sphere equivalent diameters di of individual particles.
dini / Σni) 0.63 μm, monodispersity of di (= standard deviation of di / mean of di) 19%, mean value of particle thickness hi of individual particles (= Σhini / Σni)
0.188 μm, equivalent circle diameter D of the projected area of each particle
The average value of i (= ΣDini / Σni) was 0.94 μm. (Average value of circle equivalent diameter Di) / (particle thickness hi
Average aspect ratio) was 5.

Preparation of CR-02 Except that the value of the retained pAg was changed to 7.8 in the step of adding an aqueous solution of silver nitrate and an aqueous solution of potassium bromide while maintaining the pAg constant in the method of preparing CR-01, it was exactly the same. Was prepared in the above step. The particles obtained as a result of observation by an electron microscope have an average sphere equivalent diameter di of each particle (= Σdini / Σni) of 0.63 μm and a monodispersity of di (= standard deviation of di / average value of di) 20. %,
Average value of the particle thicknesses hi of the individual particles (= {hini /}
ni) 0.150 μm, the average value (= ΣDini / Σni) of the circle equivalent diameter Di of the projected area of each particle is 1.05.
μm. The average aspect ratio defined by (average value of equivalent circle diameter Di) / (average value of particle thickness hi) was 7.

Preparation of CR-03 Except that the value of the retained pAg was set to 8.1 in the step of adding an aqueous solution of silver nitrate and an aqueous solution of potassium bromide while maintaining the pAg constant in the method of preparing CR-01, it was exactly the same. Was prepared in the above step. The particles obtained as a result of observation by an electron microscope have an average sphere equivalent diameter di of each particle (= Σdini / Σni) of 0.63 μm and a monodispersity of di (= standard deviation of di / average value of di) 19. %,
Average value of the particle thicknesses hi of the individual particles (= {hini /}
ni) 0.119 μm, and the average value (= 相当 Dini / Σni) of the circle-equivalent diameter Di of the projected area of each particle is 1.19.
μm. The average aspect ratio defined by (average value of circle equivalent diameter Di) / (average value of particle thickness hi) is 10
Met.

Preparation of CR-04 Except that the value of the retained pAg was 8.4 in the step of adding an aqueous solution of silver nitrate and an aqueous solution of potassium bromide while maintaining the pAg constant in the method of preparing CR-01, it was exactly the same. Was prepared in the step of. The particles obtained as a result of observation with an electron microscope have an average sphere equivalent diameter di of each particle (= Σdini / ０．６ni) of 0.63 μm and a monodispersity of di (= standard deviation of di / average value of di) 23. %,
Average value of the particle thicknesses hi of the individual particles (= {hini /}
ni) 0.105 μm, the average value of the circle-equivalent diameter Di of the projected area of each grain (= ΣDini / Σni) is 1.26
μm. The average aspect ratio defined by (average value of circle equivalent diameter Di) / (average value of particle thickness hi) is 12
Met.

Preparation of Internal Latent Image Type Direct Positive Silver Halide Emulsion (Step of Chemically Sensitizing Core Grain and Step of Coating with Shell) Preparation of RM1 3488 g of the core grain emulsion CR-01 was dissolved at 40 ° C. and dissolved in H _2. O
After adding 1547 ml, the pH was adjusted to 4 using an aqueous acetic acid solution.
Adjusted to 5.0 at 0 ° C. Add KBr and add pAg
Adjusted to 9.8. After raising the temperature to 75 ° C, the compound
350 mg of C-101, 4.7 mg of C-102, C
After adding 3.5 mg of -103 and aging for 90 minutes,
26.0 liters of H ₂ O, deionized gelatin 1100
g, potassium bromide 288 g. Continue with 15
0 g / l concentration of silver nitrate aqueous solution and 105 g of potassium bromide
/ L and an aqueous solution containing 11 mg / l of compound C-113 were added by the double jet method while maintaining the pAg at 7.3.
Silver nitrate was added in an amount of 2200 g while increasing the flow rate over 86 minutes so that the initial speed became 2.2 times the final speed. Subsequently, an aqueous silver nitrate solution at a concentration of 238 g / l and an aqueous potassium bromide solution at 167 g / l were added by the double jet method while maintaining the pAg at 7.3. The amount of silver nitrate added is 21
A quantity of 00 g was added over 50 minutes while accelerating the flow rate so that the initial speed was 1.5 times the final speed. After adding 550 g of potassium bromide and washing with water by the usual flocculation method, deionized gelatin and H ₂ O were added to adjust to contain 0.74 mol of silver and 60.3 g of gelatin per kg of emulsion. . The particles obtained as a result of observation with an electron microscope have an average sphere equivalent diameter di of individual particles (= Σdini / Σni) of 1.06 μm and a monodispersity of di (= standard deviation of di / average value of di). %, The average value of the particle thicknesses hi of the individual particles (= Σhini / Σni)
0.32 μm, circle equivalent diameter Di of the projected area of each particle
Was 1.58 μm (= ΣDini / Σni). The average aspect ratio defined by (average value of equivalent circle diameter Di) / (average value of particle thickness hi) was 5.

[0065] The RM2 core particle emulsion CR-01 3488g dissolved at 40 ° C. H ₂ O
After adding 1547 ml, the pH was adjusted to 4 using an aqueous acetic acid solution.
Adjusted to 5.0 at 0 ° C. Add KBr and add pAg
Adjusted to 9.8. After raising the temperature to 75 ° C, the compound
350 mg of C-101, 4.7 mg of C-102, C
After adding 3.5 mg of -103 and aging for 90 minutes,
26.0 liters of H ₂ O, deionized gelatin 1100
g, potassium bromide 288 g. Continue with 15
0 g / l concentration of silver nitrate aqueous solution and 105 g of potassium bromide
/ L and an aqueous solution containing 11 mg / l of compound C-113 were added by the double jet method while maintaining the pAg at 7.7.
Silver nitrate was added in an amount of 2200 g while increasing the flow rate over 86 minutes so that the initial speed became 2.2 times the final speed. Subsequently, an aqueous solution of silver nitrate having a concentration of 238 g / l and an aqueous solution of potassium bromide at 167 g / l were added by the double jet method while maintaining the pAg at 7.7. The amount of silver nitrate added is 21
A quantity of 00 g was added over 50 minutes while accelerating the flow rate so that the initial speed was 1.5 times the final speed. After adding 550 g of potassium bromide and washing with water by the usual flocculation method, deionized gelatin and H ₂ O were added to adjust to contain 0.74 mol of silver and 60.3 g of gelatin per kg of emulsion. . The particles obtained as a result of observation with an electron microscope have an average sphere equivalent diameter di of individual particles (= Σdini / Σni) of 1.06 μm and a monodispersity of di (= standard deviation of di / average value of di). %, The average value of the particle thicknesses hi of the individual particles (= Σhini / Σni)
0.25 μm, equivalent circle diameter Di of the projected area of each particle
Was 1.77 μm (= ｉｎDini / Σni). The average aspect ratio defined by (average value of equivalent circle diameter Di) / (average value of particle thickness hi) was 7.

[0066] The RM3 core particle emulsion CR-01 3488g dissolved at 40 ° C. H ₂ O
After adding 1547 ml, the pH was adjusted to 4 using an aqueous acetic acid solution.
Adjusted to 5.0 at 0 ° C. Add KBr and add pAg
Adjusted to 9.8. After raising the temperature to 75 ° C, the compound
350 mg of C-101, 4.7 mg of C-102, C
After adding 3.5 mg of -103 and aging for 90 minutes,
26.0 liters of H ₂ O, deionized gelatin 1100
g, potassium bromide 288 g. Continue with 15
0 g / l concentration of silver nitrate aqueous solution and 105 g of potassium bromide
/ L and an aqueous solution containing 11 mg / l of compound C-113 were added by the double jet method while maintaining the pAg at 8.2.
Silver nitrate was added in an amount of 2200 g while increasing the flow rate over 86 minutes so that the initial speed became 2.2 times the final speed. Subsequently, an aqueous silver nitrate solution having a concentration of 238 g / l and an aqueous potassium bromide solution having a concentration of 167 g / l were added by the double jet method while maintaining the pAg at 8.2. The amount of silver nitrate added is 21
A quantity of 00 g was added over 50 minutes while accelerating the flow rate so that the initial speed was 1.5 times the final speed. After adding 550 g of potassium bromide and washing with water by the usual flocculation method, deionized gelatin and H ₂ O were added to adjust to contain 0.74 mol of silver and 60.3 g of gelatin per kg of emulsion. . The particles obtained as a result of observation with an electron microscope have an average sphere equivalent diameter di of individual particles (= Σdini / Σni) of 1.06 μm and a monodispersity of di (= standard deviation of di / average value of di). %, The average value of the particle thicknesses hi of the individual particles (= Σhini / Σni)
0.21 μm, circle equivalent diameter Di of the projected area of each particle
Was 1.92 μm (= ｉｎDini / Σni). The average aspect ratio defined by (average value of equivalent circle diameter Di) / (average value of particle thickness hi) was 9.

[0067] The RM4 core particle emulsion CR-02 3488g dissolved at 40 ° C. H ₂ O
After adding 1547 ml, the pH was adjusted to 4 using an aqueous acetic acid solution.
Adjusted to 5.0 at 0 ° C. Add KBr and add pAg
Adjusted to 9.8. After raising the temperature to 75 ° C, the compound
350 mg of C-101, 4.7 mg of C-102, C
After adding 3.5 mg of -103 and aging for 90 minutes,
26.0 liters of H ₂ O, deionized gelatin 1100
g, potassium bromide 288 g. Continue with 15
0 g / l concentration of silver nitrate aqueous solution and 105 g of potassium bromide
/ L and an aqueous solution containing 11 mg / l of compound C-113 were added by the double jet method while maintaining the pAg at 8.0.
Silver nitrate was added in an amount of 2200 g while increasing the flow rate over 86 minutes so that the initial speed became 2.2 times the final speed. Subsequently, an aqueous silver nitrate solution having a concentration of 238 g / l and an aqueous potassium bromide solution having a concentration of 167 g / l were added by the double jet method while maintaining the pAg at 8.0. The amount of silver nitrate added is 21
A quantity of 00 g was added over 50 minutes while accelerating the flow rate so that the initial speed was 1.5 times the final speed. After adding 550 g of potassium bromide and washing with water by the usual flocculation method, deionized gelatin and H ₂ O were added to adjust to contain 0.74 mol of silver and 60.3 g of gelatin per kg of emulsion. . The particles obtained as a result of observation with an electron microscope have an average sphere equivalent diameter di of individual particles (= Σdini / Σni) of 1.06 μm and a monodispersity of di (= standard deviation of di / average value of di). %, The average value of the particle thicknesses hi of the individual particles (= Σhini / Σni)
0.21 μm, circle equivalent diameter Di of the projected area of each particle
Was 1.92 μm (= ｉｎDini / Σni). The average aspect ratio defined by (average value of equivalent circle diameter Di) / (average value of particle thickness hi) was 9.

[0068] The RM5 core particle emulsion CR-03 3488g dissolved at 40 ° C. H ₂ O
After adding 1547 ml, the pH was adjusted to 4 using an aqueous acetic acid solution.
Adjusted to 5.0 at 0 ° C. Add KBr and add pAg
Adjusted to 9.8. After raising the temperature to 75 ° C, the compound
350 mg of C-101, 4.7 mg of C-102, C
After adding 3.5 mg of -103 and aging for 90 minutes,
26.0 liters of H ₂ O, deionized gelatin 1100
g, potassium bromide 288 g. Continue with 15
0 g / l concentration of silver nitrate aqueous solution and 105 g of potassium bromide
/ L and an aqueous solution containing 11 mg / l of compound C-113 were added by the double jet method while maintaining the pAg at 7.5.
Silver nitrate was added in an amount of 2200 g while increasing the flow rate over 86 minutes so that the initial speed became 2.2 times the final speed. Subsequently, an aqueous solution of silver nitrate having a concentration of 238 g / l and an aqueous solution of potassium bromide at 167 g / l were added by the double jet method while maintaining the pAg at 7.7. The amount of silver nitrate added is 21
A quantity of 00 g was added over 50 minutes while accelerating the flow rate so that the initial speed was 1.5 times the final speed. After adding 550 g of potassium bromide and washing with water by the usual flocculation method, deionized gelatin and H ₂ O were added to adjust to contain 0.74 mol of silver and 60.3 g of gelatin per kg of emulsion. . The particles obtained as a result of observation with an electron microscope have an average sphere equivalent diameter di of individual particles (= Σdini / Σni) of 1.06 μm and a monodispersity of di (= standard deviation of di / average value of di). %, The average value of the particle thicknesses hi of the individual particles (= Σhini / Σni)
0.21 μm, circle equivalent diameter Di of the projected area of each particle
Was 1.92 μm (= ｉｎDini / Σni). The average aspect ratio defined by (average value of equivalent circle diameter Di) / (average value of particle thickness hi) was 9.

[0069] The RM6 core particle emulsion CR-03 3488g dissolved at 40 ° C. H ₂ O
After adding 1547 ml, the pH was adjusted to 4 using an aqueous acetic acid solution.
Adjusted to 5.0 at 0 ° C. Add KBr and add pAg
Adjusted to 9.8. After raising the temperature to 75 ° C, the compound
350 mg of C-101, 4.7 mg of C-102, C
After adding 3.5 mg of -103 and aging for 90 minutes,
26.0 liters of H ₂ O, deionized gelatin 1100
g, potassium bromide 288 g. Continue with 15
0 g / l concentration of silver nitrate aqueous solution and 105 g of potassium bromide
/ L and an aqueous solution containing 11 mg / l of compound C-113 were added by the double jet method while maintaining the pAg at 7.3.
Silver nitrate was added in an amount of 2200 g while increasing the flow rate over 86 minutes so that the initial speed became 2.2 times the final speed. Subsequently, an aqueous silver nitrate solution at a concentration of 238 g / l and an aqueous potassium bromide solution at 167 g / l were added by the double jet method while maintaining the pAg at 7.3. The amount of silver nitrate added is 21
A quantity of 00 g was added over 50 minutes while accelerating the flow rate so that the initial speed was 1.5 times the final speed. After adding 550 g of potassium bromide and washing with water by the usual flocculation method, deionized gelatin and H ₂ O were added to adjust to contain 0.74 mol of silver and 60.3 g of gelatin per kg of emulsion. . The particles obtained as a result of observation with an electron microscope have an average sphere equivalent diameter di of individual particles (= Σdini / Σni) of 1.06 μm and a monodispersity of di (= standard deviation of di / average value of di). %, The average value of the particle thicknesses hi of the individual particles (= Σhini / Σni)
0.25 μm, equivalent circle diameter Di of the projected area of each particle
Was 1.77 μm (= ｉｎDini / Σni). The average aspect ratio defined by (average value of equivalent circle diameter Di) / (average value of particle thickness hi) was 7.

[0070] The RM7 core particle emulsion CR-02 3488g dissolved at 40 ° C. H ₂ O
After adding 1547 ml, the pH was adjusted to 4 using an aqueous acetic acid solution.
Adjusted to 5.0 at 0 ° C. Add KBr and add pAg
Adjusted to 9.8. After raising the temperature to 75 ° C, the compound
350 mg of C-101, 4.7 mg of C-102, C
After adding 3.5 mg of -103 and aging for 90 minutes,
26.0 liters of H ₂ O, deionized gelatin 1100
g, potassium bromide 288 g. Continue with 15
0 g / l concentration of silver nitrate aqueous solution and 105 g of potassium bromide
/ L and an aqueous solution containing 11 mg / l of compound C-113 were added by the double jet method while maintaining the pAg at 8.4.
Silver nitrate was added in an amount of 2200 g while increasing the flow rate over 86 minutes so that the initial speed became 2.2 times the final speed. Subsequently, an aqueous solution of silver nitrate having a concentration of 238 g / l and an aqueous solution of potassium bromide at 167 g / l were added by the double jet method while maintaining the pAg at 8.4. The amount of silver nitrate added is 21
A quantity of 00 g was added over 50 minutes while accelerating the flow rate so that the initial speed was 1.5 times the final speed. After adding 550 g of potassium bromide and washing with water by the usual flocculation method, deionized gelatin and H ₂ O were added to adjust to contain 0.74 mol of silver and 60.3 g of gelatin per kg of emulsion. . The particles obtained as a result of observation with an electron microscope have an average sphere equivalent diameter di of individual particles (= Σdini / Σni) of 1.06 μm and a monodispersity of di (= standard deviation of di / average value of di). %, The average value of the particle thicknesses hi of the individual particles (= Σhini / Σni)
0.16 μm, circle equivalent diameter Di of the projected area of each particle
Has an average value (= ΣDini / Σni) of 2.23 μm,
The average aspect ratio defined by (average value of equivalent circle diameter Di) / (average value of particle thickness hi) was 14.

[0071] The RM8 core particle emulsion CR-03 3488g dissolved at 40 ° C. H ₂ O
After adding 1547 ml, the pH was adjusted to 4 using an aqueous acetic acid solution.
Adjusted to 5.0 at 0 ° C. Add KBr and add pAg
Adjusted to 9.8. After raising the temperature to 75 ° C, the compound
350 mg of C-101, 4.7 mg of C-102, C
After adding 3.5 mg of -103 and aging for 90 minutes,
26.0 liters of H ₂ O, deionized gelatin 1100
g, potassium bromide 288 g. Continue with 15
0 g / l concentration of silver nitrate aqueous solution and 105 g of potassium bromide
/ L and an aqueous solution containing 11 mg / l of the compound C-113 were added by the double jet method while maintaining the pAg at 7.6.
Silver nitrate was added in an amount of 2200 g while increasing the flow rate over 86 minutes so that the initial speed became 2.2 times the final speed. Subsequently, an aqueous silver nitrate solution at a concentration of 238 g / l and an aqueous potassium bromide solution at 167 g / l were added by the double jet method while maintaining the pAg at 8.6. The amount of silver nitrate added is 21
A quantity of 00 g was added over 50 minutes while accelerating the flow rate so that the initial speed was 1.5 times the final speed. After adding 550 g of potassium bromide and washing with water by the usual flocculation method, deionized gelatin and H ₂ O were added to adjust to contain 0.74 mol of silver and 60.3 g of gelatin per kg of emulsion. . The particles obtained as a result of observation by an electron microscope have an average value of the equivalent spherical diameters di of the individual particles (= Σdini / Σni) (ni indicates the number of particles of the type i) 1.06 μm, monodispersity of di (= Standard deviation of di / average value of di) 22%, average value of the particle thicknesses hi of individual particles (= ｉhini / Σni) 0.16 μm
m, the average value of the circle equivalent diameter Di of the projected area of each particle (= ΣDini / Σni) is 2.23 μm, and is defined as (average value of circle equivalent diameter Di) / (average value of grain thickness hi). The average aspect ratio was 14.

[0072] The RM9 core particle emulsion CR-04 3488g dissolved at 40 ° C. H ₂ O
After adding 1547 ml, the pH was adjusted to 4 using an aqueous acetic acid solution.
Adjusted to 5.0 at 0 ° C. Add KBr and add pAg
Adjusted to 9.8. After raising the temperature to 75 ° C, the compound
350 mg of C-101, 4.7 mg of C-102, C
After adding 3.5 mg of -103 and aging for 90 minutes,
26.0 liters of H ₂ O, deionized gelatin 1100
g, potassium bromide 288 g. Continue with 15
0 g / l concentration of silver nitrate aqueous solution and 105 g of potassium bromide
/ L and an aqueous solution containing 11 mg / l of compound C-113 were added by the double jet method while maintaining the pAg at 7.4.
Silver nitrate was added in an amount of 2200 g while increasing the flow rate over 86 minutes so that the initial speed became 2.2 times the final speed. Subsequently, an aqueous silver nitrate solution at a concentration of 238 g / l and an aqueous potassium bromide solution at 167 g / l were added by the double jet method while maintaining the pAg at 8.6. The amount of silver nitrate added is 21
A quantity of 00 g was added over 50 minutes while accelerating the flow rate so that the initial speed was 1.5 times the final speed. After adding 550 g of potassium bromide and washing with water by the usual flocculation method, deionized gelatin and H ₂ O were added to adjust to contain 0.74 mol of silver and 60.3 g of gelatin per kg of emulsion. . The particles obtained as a result of observation with an electron microscope have an average sphere equivalent diameter di of individual particles (= Σdini / Σni) of 1.06 μm and a monodispersity of di (= standard deviation of di / average value of di). %, The average value of the particle thicknesses hi of the individual particles (= Σhini / Σni)
0.16 μm, circle equivalent diameter Di of the projected area of each particle
Has an average value (= ΣDini / Σni) of 2.23 μm,
The average aspect ratio defined by (average value of equivalent circle diameter Di) / (average value of particle thickness hi) was 14.

Surface Chemical Sensitization Emulsions RM1 to RM9 were each adjusted to have pAg of 9.2 and p
After adjusting H to 6.5, the following surface chemical sensitization was performed. Compounds C-106 and C-107 were each converted to 1 mol of silver
5.8 × 10 ^-6 mol, 1.2 × 10 ^-4 mol per 1
(C-107 is one repeating unit as 1 mol)
After the addition, the mixture was aged at 70 ° C for 60 minutes. Subsequently, 5.8 × 10 ⁻³ mol of potassium bromide was added per 1 mol of silver, and the compounds C-108, C-109, C-110 and C were added.
3.-111 and C-112 were added per mol of silver.
3 × 10 ⁻⁵ mol, 2.6 × 10 ⁻⁵ mol, 1.3 × 1
0 ^-4 mol, 4.0 × 10 ^-6 mol, 2.4 × 10 ^-5 m
After aging for 20 minutes, the mixture was cooled and stored.
C-108, C-109, C-110, C-111,
C-112 is a sensitizing dye. C-108 is an aqueous solution,
C-109, C-110, C-111, and C-112 were added in the form of mixing these powders, adding them to a 5% aqueous gelatin solution, and then dispersing them with a dissolver. The compounds used in the preparation of the emulsion are summarized below.

[0074]

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[0075]

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[0076]

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Table 1 shows a list of the emulsions prepared in this example.

[0078]

[Table 1]

Preparation of Multilayer Coated Samples Coated samples having the structures shown in Tables 2 to 5 below were prepared.

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

[Table 4]

[0083]

[Table 5]

In Table 4, the internal latent type direct positive emulsions used in the eighth layer are the emulsions RM1 to RM9 prepared in this example, and the color diffusion transfer photosensitive material samples obtained by using these emulsions were used. Samples 101 to 109 were used, respectively. Table 6 lists the emulsions used for the other emulsion layers. Each emulsion can be prepared with reference to the examples of JP-A-6-51423.

[0085]

[Table 6]

A sensitizing dye was added immediately before the completion of surface chemical sensitization. Table 7 shows the amounts and methods of adding the sensitizing dyes.

[0087]

[Table 7]

The compounds used in preparing the multilayer sample are shown below.

[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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The cover sheet was prepared as follows. The following layers were coated on a gelatin-primed polyethylene terephthalate support containing a light piping inhibitor dye. (A) 10.4 g of an acrylic acid / n-butyl acrylate copolymer (80/20 (mol%)) having an average molecular weight of 50,000
/ M ² and 1,4-bis (2,3-epoxypropoxy) - butane 0.1 g / m ² comprises a neutralizing layer. (B) 4.3 g of cellulose acetate having a degree of acetylation of 55%
/ M ² and a methyl vinyl ether / maleic anhydride copolymer (50/50 (mol%)) methyl half ester 0.2 g / m ² comprising the layer (c) average molecular weight 25,000 of n- butyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid copolymer (66.1 / 28.4 / 5.5 (% by mass)) was added in an amount of 0.3 g / m ² and an average molecular weight of 40,000 ethyl methacrylate / 2-hydroxyethyl methacrylate / Acrylic acid copolymer (66.1 / 28.4 / 5.5 (% by mass))
And 0.8 g / m ² . KAYASE made by Nippon Kayaku Co., Ltd.
A combination of T GREEN AG and the following compounds in a ratio of 3: 1 was used.

[0103]

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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 which can be broken by pressure. 695 g of water 1-p-tolyl-4-hydroxymethyl-4-methyl 7.00 g-3-pyrazolidin-1-one 1-phenyl-4-hydroxymethyl-4-methyl 9.85 g-3-pyrazolidin-1-one Sulfinic acid polymer 2.10 g 5-methylbenzotriazole 2.50 g Zinc nitrate hexahydrate 0.60 g Potassium sulfite 1.90 g Aluminum nitrate nonahydrate 0.60 g Carboxymethylcellulose Na salt 56.0 g Potassium hydroxide 55.0 g Carbon black 160 g Anionic surfactant 8.60 g Anionic surfactant 0.03 g Alkyl-modified PVA (manufactured by Kuraray Co., Ltd.) 0.06 g Cationic polymer 1.05 g

[0105]

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[0106] Samples 101 to 1
After exposing 09 from the emulsion layer side through a continuous gray wedge and superimposing it on the cover sheet, the processing solution was spread between the two using a pressure roller to a thickness of 62 μm. Exposure was performed at 1/10000 second exposure. As going from the low-exposure side to the high-exposure side, the color density is such that the tone of the negative image appears from the highest saturation density Dmax through the tone portion of the positive image, the Dmin portion of the lowest density, and then reaches the highest saturation density again. Made a change. (This portion is referred to as a reversal negative image.) The temperature during the developing process was kept at 25 ° C. The measurement was performed with an R filter. The sensitivity of the gradation part of the positive image is defined as positive sensitivity,
It was defined as the reciprocal of the exposure amount that gives an intermediate density between Dmax and Dmin in the positive gradation portion. The sensitivity of the reinverted negative image portion is called high illuminance negative sensitivity, and Dmin of the reinverted negative image gradation
It was defined as the reciprocal of the exposure amount giving +0.2. Table 8 shows the positive sensitivity and the high illuminance negative sensitivity of each sample. All samples 1
It is represented by a relative value with the value of 01 being 100. The foot sensitivity was defined as the reciprocal of the exposure amount giving a density of Dmin + 0.2 of the gradation of the positive image. Table 8 shows the ratio S ₁ / S _F between the foot sensitivity S ₁ after storage at 25 ° C. and 60% for one year and the foot sensitivity S _F immediately after application.

[0107]

[Table 8]

The following becomes clear from Table 8. From the results of Samples 101, 102, and 103, increasing the aspect ratio of the final grains without considering the aspect ratio of the core grain emulsion hardly leads to an improvement in the positive sensitivity, and a high illuminance negative image which is a serious problem in practical use. Greatly increase the sensitivity. At the same time, there is a large decrease in sensitivity over time. From the comparison of the samples 103, 104 and 105, in the region where the aspect ratio of the final particle is 9, the positive sensitivity is improved as the aspect ratio of the core particle is increased, and the high illuminance negative sensitivity is decreased and the sensitivity is caused by the storage time. When the aspect ratio of the core particles is 8 or more, high positive sensitivity can be realized while high illuminance negative sensitivity is sufficiently low for practical use. At the same time, the decrease in sensitivity due to storage time is remarkably improved. Sample 1
The positive sensitivity does not improve even if the aspect ratio of the core particle is increased from the comparison of 02 and 106. Samples 107, 108, 1
From the comparison of 09, when the aspect ratio of the core particle is high even in the region where the aspect ratio of the final particle is 14, the positive sensitivity is improved and the high illuminance negative sensitivity is reduced. When the aspect ratio of the core particles is 8 or more, high positive sensitivity can be realized while high illuminance negative sensitivity is sufficiently low for practical use. At the same time, the decrease in sensitivity due to storage time is remarkably improved. From the above, it is apparent that in the internal latent image type direct positive silver halide emulsion having an aspect ratio of 8 or more, when the aspect ratio of the core grains is 8 or more, the positive sensitivity can be improved without increasing the high illuminance negative sensitivity. became.

Example 2 In this example, unless otherwise specified, the same reference numerals as in Example 1 indicate that the same compound or emulsion was used. Preparation of RMs 11 to 19 (Step of chemically sensitizing core grains) After dissolving 3488 g of core grain emulsion CR-03 at 40 ° C and adding 1547 ml of H ₂ O, the pH was adjusted to 5.0 at 40 ° C using an aqueous acetic acid solution. Was adjusted to Further, KBr was added to adjust the pAg to 9.8.
After raising the temperature to 75 ° C, compound C-101 was added to 350
mg, C-102 4.7 mg, C-103 3.5 m
After aging for 90 minutes, 26.0 liters of H ₂ O, 1100 g of deionized gelatin, 2 parts of potassium bromide were added.
88 g were added.

(Step of coating with shell) An aqueous solution containing silver nitrate at a concentration of 150 g / l and an aqueous solution containing 105 g / l of potassium bromide were added by the double jet method while maintaining the pAg at 7.6. Silver nitrate was added in an amount of 2200 g while increasing the flow rate over 86 minutes so that the initial speed became 2.2 times the final speed. Subsequently, a silver nitrate aqueous solution having a concentration of 238 g / l and an aqueous potassium bromide solution having a concentration of 167 g / l were pAg 7.6.
And added by the double jet method. The initial speed of the final speed was 1.
The addition was performed while accelerating the flow rate so as to increase the flow rate by five times. At the same time as adding the silver nitrate aqueous solution, C was added to 1 mol of silver nitrate.
-113 was added while accelerating the flow rate so as to be added while maintaining the ratio of adding 3.5 × 10 ⁻⁵ mol. By changing the start and end times of addition of C-113, four types of emulsions RM11 to RM14 in which C-113 was localized in various parts of the grains were prepared. At the same time as adding the silver nitrate aqueous solution, C-113 was added to 1 mol of silver nitrate.
Was added while accelerating the flow rate so as to maintain the ratio of 7 × 10 ⁻⁵ mol. C-113
The two types of emulsions RM15 in which C-113 is localized in various parts of the grains by changing the start and end timings of
Was prepared from

While maintaining the ratio of adding 1.7 × 10 ⁻⁵ mol of C-113 at the same time as adding 1 mol of silver nitrate, C-113 was added over the entire region from the addition of silver nitrate to the end. Was added uniformly over the entire area of the particles to prepare RM17. In addition, C-113 was added over the entire region from the addition of silver nitrate to the end thereof while maintaining the ratio of adding 3.5 × 10 ⁻⁵ mol of C-113 at the same time as adding 1 mol of silver nitrate. RM18 uniformly added over the entire area was prepared. 1m silver nitrate
ol was added and C-113 was 0.7 × 10
^While maintaining the ratio that ^-5 mol was added, silver nitrate was added over the entire region from the addition to the end thereof to prepare RM19 in which C-113 was uniformly added over the entire region of the grains. RM
For each of Nos. 11 to RM19, 550 g of potassium bromide was added, washed with water by a usual flocculation method, deionized gelatin and H ₂ O were added, and emulsion 1k was added.
It was adjusted to contain 0.74 mol silver / g and 60.3 g gelatin / g.

The particles obtained as a result of observation by an electron microscope have an average value (= Σdini) of the equivalent spherical diameters di of the individual particles.
/ Σni) 1.06 μm, monodispersity of di (= standard deviation of di / mean value of di) 22%, mean value of particle thickness hi of individual particles (= Σhini / Σni) 0.32 μm,
Average value of the circle equivalent diameter Di of the projected area of each particle (= Σ
Dini / Σni) was 1.58 μm. The average aspect ratio defined by (average value of equivalent circle diameter Di) / (average value of particle thickness hi) was 9. These emulsions were subjected to the same chemical sensitization as in Example 1. That is, after adjusting the pAg to 9.2 and the pH to 6.5, respectively, the compounds C-106 and C-107 were respectively adjusted to 5.8 × 10 ⁻⁶ mol and 1.2 × 10 ⁻⁴ mol per mol of silver (C -1
07 was added as 1 mol of a repeating unit) and then aged at 70 ° C. for 60 minutes. Subsequently, 5.8 × 10 ^-3 mol of potassium bromide was added per 1 mol of silver, and compounds C-108, 109, 110, 111 and 112 were each added at 4.3 × 10 ^-5 mol and 2.6 per mol of silver.
× 10 ⁻⁵ mol, 1.3 × 10 ⁻⁴ mol, 4.0 × 10
^-6 mol, 2.4 × 10 ^-5 mol, and after aging for 20 minutes, cooled and stored.

A multilayer coating sample similar to that prepared in Example 1 was prepared. The emulsion of the eighth layer was the emulsion RM11 of this example.
Color Diffusion Transfer Photosensitive Material Sample 2
01 to 209. The same exposure and processing were performed in combination with the same cover sheet as in Example 1 to obtain positive sensitivity and high illuminance negative sensitivity. At the same time, a similar experiment was performed in Example 1.
Specimens 101 and 105 were also used. The results are shown in Table 9. The numerical values are relative values with the value of the sample 101 being 100.

[0114]

[Table 9]

Table 9 shows the following. Samples 201 to 2 using the emulsion of the present invention as compared with Sample 101
09 indicates that the positive sensitivity is high. However, from the results of Samples 209, 208, and 207, when Compound C-113 is added uniformly between particles, the positive sensitivity becomes high at the optimum amount of addition, but the high illuminance negative sensitivity becomes high. It is a problem. From the comparison of Samples 201 to 207, the positive sensitivity can be sensitized without increasing the high illuminance negative sensitivity if the addition amount of the compound C-113 is set to 60% or less of the silver amount used in the step of coating with the shell.

[0116]

According to the present invention, an internal latent image type direct positive silver halide emulsion having a high sensitivity of a positive image, a low sensitivity of a reversal negative image, and a small desensitization during storage, and the same. It can be seen that a color diffusion transfer photosensitive material using the same is obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 8/10 504 G03C 8/10 504

Claims (3)

[Claims] The tabular silver halide grains have an average aspect ratio of 8 or more, and the tabular silver halide grains form a core grain, a step of subjecting the core grain to chemical sensitization, and a step of forming a shell. An internal latent image type direct positive silver halide emulsion, wherein the core grains are tabular grains having an average aspect ratio of 8 or more, wherein the internal latent image type direct positive silver halide emulsion is formed through a coating step. . 2. At least one of the metal complexes represented by the following general formula (I) is added as a localized layer to a region of 0 to 60% of silver used in the step of coating with the shell. 2. The tabular internal latent image type direct positive silver halide emulsion according to claim 1, wherein: General formula (I) [M (CN) _6-a L _a ] ^{n- wherein} M: Fe, Ru, Ir, Co, Cr, Mn, R
h, Re, Osa a: 0, 1 or 2 L: ligand other than CN n: 2, 3 or 4 3. A support comprising at least one light-sensitive silver halide emulsion layer combined with a dye-forming substance, wherein the dye-forming substance is represented by the following general formula (II): In a color diffusion transfer photosensitive material which is a non-diffusible compound that releases a diffusible dye or a precursor thereof, or a compound that changes its diffusivity, at least one of the silver halide emulsion layers is a compound. 1 or 2
A color diffusion transfer photosensitive material comprising the tabular internal latent image type direct positive silver halide emulsion described in any one of the above. General formula (II) (DYE-Y) _n -Z ｛DYE represents a dye group, a temporarily shortened dye or dye precursor group, Y represents a simple bond or a linking group, and Z represents a silver developing compound. Relatedly, it represents a group having a property of releasing a diffusible dye or a precursor thereof, or a group having a property of causing a difference in diffusivity of a compound represented by (DYE-Y) _n -Z, wherein n is 1 or 2 and when n is 2, the two DYE-Ys may be the same or different. ｝