JPH07333770A - Direct positive silver halide emulsion and color diffusion transfer photographic material using same - Google Patents

Abstract

PURPOSE:To provide an internal latent image type direct positive silver halide emulsion excellent in fabrication stability and to provide a color diffusion transfer photographic material using the same. CONSTITUTION:This internal latent image type direct positive silver halide emulsion is prepared using a seed crystal emulsion prepared via a demineralizing process; is prepared by using as a seed crystal emulsion a silver halide emulsion which is characterized in that it contains flake silver halide particles by 50% or more of all the silver halide particles, the flake silver halide particles having an average particle diameter of 0.3mum or more and an aspect ratio (the diameter of silver halide particle equivalent to a circle/particle thickness) of 2 to 100 inclusive; and contains the flake silver halide particles by 50%, or more of all the silver halide particles, the flake silver halide particles having an aspect ratio (the diameter of silver halide particle equivalent to a circle/particle thickness) of 2 to 100 inclusive.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art The photographic method using silver halide has excellent sensitivity and gradation characteristics as compared with other photographic methods such as electrophotographic method and diazo photographic method, and has been widely used. . Among them, a method of directly forming a positive image is known. This is described, for example, in US Pat.
No. 76 and Japanese Patent Publication No. 60-55821, an internal latent image type direct positive silver halide emulsion is developed by a surface developing solution (a latent image forming site inside a silver halide grain is substantially left undeveloped. When developing with a liquid, a positive image is obtained by giving uniform exposure or by using a nucleating agent. Such a direct positive silver halide emulsion is superior to the negative type emulsion in that a positive image can be obtained by a single processing. Generally, in an internal latent image type direct positive silver halide emulsion, a silver halide grain (hereinafter also referred to as a core grain) is formed by mixing a soluble silver salt and a soluble halide in an aqueous gelatin solution. Is chemically sensitized, followed by silver halide deposition for shell formation, then desalting and, if necessary, chemical sensitization. For example, Japanese Examined Patent Publication Sho-52-342
No. 13 (US Pat. No. 3,761,276) describes an internal latent image type emulsion useful as a direct positive emulsion.
This emulsion is characterized in that it contains a doping agent inside the silver halide grain and chemically sensitizes the grain surface.
This is also shown in US Pat. No. 3,317,322 to Porter et al.

On the other hand, the present invention also relates to tabular silver halide emulsions (hereinafter abbreviated as tabular emulsions). Regarding tabular emulsions, Cleve, Photography Theory has already been written by Cleve. and Practice
(1930)), 131; Gatov, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), 14th
Volume 248-257 (1970); U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
33,048, 4,439,520, 4,41
No. 4,306, No. 4,459,353, British Patent No. 2,112,157, Japanese Unexamined Patent Publication No. 59-99433, No. 62-209445, and the like, their manufacturing methods and use techniques are disclosed. In particular, a tabular internal latent image type direct positive silver halide emulsion is described in US Pat. No. 4,395,478.
And 4,504,570, 4,996,137
Japanese Patent Publication No. 64-8327, JP-A-1-131547.
No. 1,154,142, and No. 1,154,842.
No. 9, JP-A-1-297649, and the like. These tabular internal latent image type direct positive emulsions are excellent in that they have a good sharpness, a rapid development progress, and a direct positive image having a small development temperature dependency. Regarding the method for preparing a tabular emulsion, JP-A Nos. 58-113927 and 58-1.
No. 13928, No. 58-127921, JP-A-1-1.
No. 58426 and the like can be referred to, but the tabular emulsions prepared according to these methods had a long time required for the grain forming step and had a major problem in terms of productivity. In addition, the scale dependence and reproducibility at the time of grain formation were not always satisfactory. In particular, the tabular internal latent image type direct positive emulsion was poor in reproducibility of preparation because its preparation process was complicated and took a long time. On the other hand, as a means for stabilizing the grain forming step, there is a so-called seed crystal method of growing separately prepared seed crystal grains, but there is no example applied to the internal latent image type direct positive emulsion. As a method of preparing tabular grains by a seed crystal method, Japanese Patent Publication No. 3-46811 discloses a grain forming method using a spherical seed crystal (aspect ratio 1). The aspect ratio is 3.0 or less, and particles having a high aspect ratio cannot be obtained. Further, JP-A-61-1112142, JP-A-62-58237 and JP-A-5-112237.
No. 5-142329 discloses a grain forming method using multiple twin grains. This method is suitable for the preparation of tabular grains having a high aspect ratio, but there is a problem in terms of stable preparation because performance fluctuations occur unless the desalted and redispersed seed crystals are promptly grown.

Further, JP-A-3-196136 and JP-A-3-196136.
No. 196137 discloses a technique of forming grains in the presence of an oxidizing agent for silver, but no example of applying this technique to the preparation of seed crystal emulsion is known. As described above, although the stabilization of preparation of the internal latent image type direct positive silver halide emulsion, particularly the tabular internal latent image type direct positive silver halide emulsion is a big problem, a good solution has been found. Didn't.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an internal latent image type direct positive silver halide emulsion (particularly a tabular internal latent image type direct positive silver halide emulsion) excellent in manufacturing stability and the same. It is to provide a color diffusion transfer photosensitive material using.

[0006]

The objects of the present invention are as follows.
This was achieved by the internal latent image type direct positive silver halide emulsions of (1) to (5) and the color diffusion transfer light-sensitive material using the same. (1) An internal latent image type direct positive silver halide emulsion prepared by using a seed crystal emulsion prepared through a desalting step. (2) Average particle diameter of 0.3 μm prepared through desalting process
Above, aspect ratio (diameter equivalent to circle of silver halide grain /
Aspect ratio (prepared using a silver halide emulsion characterized by containing tabular silver halide grains having a grain thickness of 2 or more and 100 or less in an amount of 50% or more of all silver halide grains as a seed crystal emulsion) An internal latent image type direct positive silver halide containing 50% or more of tabular silver halide grains having a circle equivalent diameter of silver halide grains / grain thickness of 2 to 100. emulsion. (3) In the internal latent image type direct positive silver halide emulsion according to the above (1) or (2), the seed crystal emulsion contains at least one oxidizing agent for silver. Silver halide emulsion. (4) In the internal latent image type direct positive silver halide emulsion described in (3) above, the oxidizing agent is a compound selected from the compounds represented by the following general formulas [A], [B] and [C]. Internal latent image type direct positive silver halide emulsion characterized by.

[0007]

[Chemical 2]

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

The specific structure of the present invention will be described in detail below. The present invention is applied to internal latent image type direct positive silver halide emulsions. An internal latent image type direct positive silver halide emulsion (hereinafter sometimes abbreviated as an internal latent image type silver halide emulsion) means that a latent image is mainly formed inside a silver halide grain when imagewise exposed. A silver halide emulsion, specifically, a silver halide emulsion is coated on a transparent support in a fixed amount, and exposed to light for a fixed time of 0.01 to 1 second. 2 in "internal" developer)
The maximum density obtained when developed at 0 ° C. for 5 minutes is the same as when the second sample exposed as described above was developed at 20 ° C. for 5 minutes in the following developer B (“surface type” developer). Defined as having a concentration at least 5 times greater than the maximum concentration obtained. Here, the maximum density is measured by a usual photographic density measuring method. Developer A N-methyl-p-aminophenol sulfite 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Sodium carbonate (monohydrate) 52.5g Potassium bromide 5g Potassium iodide 0.5g Water added 1 liter Developer B N-methyl-p-aminophenol sulfite 2.5 g 1-ascorbic acid 10 g potassium metanitrate 35 g potassium bromide 1 g Water added 1 liter As an internal latent image type silver halide emulsion, for example, US Pat. , 953 and 2,592,250, etc., and conversion type silver halide emulsions, and the first and second phases as described in US Pat. No. 3,935,014. Laminated structure type silver halide emulsion with different halogen composition, or dope metal ion,
Alternatively, a core / shell type silver halide emulsion obtained by coating a chemically sensitized core grain with a shell may be used. Of these, a core / shell type silver halide emulsion is particularly preferable as the internal latent image type silver halide emulsion used in the present invention, and examples thereof include U.S. Pat. Nos. 3,206,313 and 3,31.
7,322, 3,761,266, 3,76
1,276, 3,850,637, 3,92
No. 3,513, No. 4,035,185, No. 4,18
No. 4,878, No. 4,395,478, No. 4,504,
570, JP-A-57-136641 and 61-31.
37, JP-A-61-299155, JP-A-62-208
241 etc. are mentioned. In order to directly obtain a positive image, a uniform second exposure is applied to the front surface of the exposed layer after the above-mentioned internal latent image type silver halide emulsion is imagewise exposed and before or during the development treatment (the "light fog method"). Development process in the presence of a nucleating agent ("chemical fogging", e.g. Research Disclosur, U.S. Pat. No. 1,151,363).
e), Volume 151, No. 15162, pp. 76-78), the method of directly obtaining a positive image by the "chemical fogging method" is preferred in the present invention. The nucleating agent used in the present invention will be described below. As described above, in order to directly obtain a positive image using the internal latent image type silver halide emulsion, after the image exposure, before the development processing or during the development processing, the entire surface is uniformly exposed to the second exposure, or It is obtained by carrying out development processing in the presence of a nucleating agent. As the nucleating agent, US Patents 2,563,785 and 2,5
88,982, hydrazines, US Pat.
227,552, hydrazides and hydrazones, British Patent 1,283,835, JP-A-52-696.
13, No. 55-138742, No. 60-11837.
No. 62-210451 and 62-291637.
U.S. Pat. Nos. 3,615,515 and 3,719,49.
4, the same 3,734,738, the same 4,094,683, the same 4,115,122, the same 4306016, the same 44710
44, etc., heterocyclic quaternary salt compounds, US Pat.
718,470, a sensitizing dye having a nucleating substituent in a dye molecule, U.S. Pat. No. 4,030,9.
25, 4,031,127, 4,245,037,
Same as 4,255,511, Same as 4,266,013, Same as 4,
276,364, thiourea-bonded acylhydrazine compounds described in British Patent 2,012,443, and U.S. Pat. Nos. 4,080,270 and 4,278,748,
Sialhydrazine compounds described in British Patent No. 2,011,391B and the like in which a heterocyclic group such as a thioamide ring or a triazole or a tetrazole is bonded as an adsorption group are used. The amount of the nucleating agent used here is preferably an amount that gives a sufficient maximum density when the internal latent image type emulsion is developed with a surface developing solution. In practice, the appropriate content may vary over a wide range since it depends on the characteristics of the silver halide emulsion used, the chemical structure of the nucleating agent and the development conditions, but the silver content in the internal latent silver halide emulsion may vary. 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 steps of preparing a silver halide emulsion in the present invention are roughly classified into a step of preparing a seed crystal emulsion and a step of preparing an internal latent image type direct positive silver halide emulsion including growth of seed crystal grains. Here, the seed crystal emulsion preparation process includes a grain formation process including nucleation, physical ripening, and growth, followed by a desalting and washing process. Further, the internal latent image type direct positive silver halide emulsion preparation step including the growth of seed crystal grains means the step of further growing the grains in the presence of the seed crystal grains (core grain forming step) and the subsequent core chemistry. It consists of a sensitization process, a shell formation process, a desalting / washing process, a shell chemical sensitization process, and the like. The seed crystal grains may be immediately chemically sensitized and then subjected to subsequent process treatment.

Next, the seed crystal particles of the present invention will be described in detail. In the present invention, seed crystal particles of various shapes can be used. As an example, those having a regular crystal form such as a cube, octahedron, tetradecahedron and rhombic dodecahedron, and those having an irregular crystal form such as a sphere and a plate, One having the following plane ((hk1) plane), or a mixture of grains of these crystal forms can be mentioned.
The details are the same as the grain shape of the internal latent image type direct positive silver halide emulsion described later, but it is particularly effective when a tabular seed crystal emulsion is used. Regarding the tabular seed crystal emulsion, the average grain diameter is 0.3 μm or more, and the aspect ratio (diameter equivalent to circle of silver halide grain / grain thickness) is 2.0 or more 10
The tabular silver halide grains having a number of 0 or less, preferably 2.0 or more and 10.0 or less, and particularly preferably 3.0 or more and 8.0 or less are 50% of the projected area of all the silver halide grains in the emulsion.
% Silver halide emulsion characterized by containing at least
The silver halide emulsion is preferably 70% or more, particularly preferably 85% or more. The average equivalent spherical diameter of the tabular seed crystal grains of the present invention is preferably 1.5 μm or less, particularly preferably 0.2 μm or more and 1.0 μm or less. Further, the average particle thickness of the tabular seed crystal particles of the present invention,
It is preferably 1.5 μm or less, particularly preferably 0.50 μm or less.

The tabular seed crystal grains of the present invention may be any of silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver iodochlorobromide and silver iodochloride. Silver, silver iodobromide, silver chloride,
Silver chlorobromide is preferred, and silver bromide is particularly preferred.

The tabular seed crystal grains of the present invention may have at least two layered structures having substantially different halogen compositions, or may have a uniform composition. The particle size distribution is preferably monodisperse, and the coefficient of variation is 2
0% or less is preferable.

Next, a method for preparing the tabular seed crystal emulsion of the present invention will be described. The present invention includes a step of forming tabular core grains by simultaneously mixing an aqueous solution of a water-soluble silver salt and an aqueous solution of a halide salt in a reaction vessel in which an aqueous solution of gelatin is present and further aging. Further included is the step of growing the tabular nucleus grains thus obtained. Further, a method of supplying a part or all of silver added in the grain growth process as fine particles of silver halide as described in JP-A-62-99751 can be used. The tabular seed crystal emulsion of the present invention can be prepared by referring to the publicly known method of preparing a tabular silver halide emulsion described later, except that the method of using the silver salt specified in the present invention is followed.

In the present invention, it is essential that the tabular seed crystal emulsion is washed with water for desalting and dispersed in a newly prepared protective colloid. The washing and dispersing steps will be described in detail later.

Next, the internal latent image type direct positive silver halide emulsion preparation process including the growth of seed crystal grains of the present invention will be described. The amount of the seed crystal emulsion used at this time is arbitrary, but may be 5 times or less the silver molar amount with respect to the amount of the silver salt supplied for growth, but 2 times or less, It is preferably 1 time or less, particularly preferably 1/10 or less. Further, any time can be selected from the time the seed crystal emulsion is prepared to the time it is used for growth, but it is preferable to use the seed crystal emulsion after refrigerated storage for 1 day or more. The growth in the presence of seed crystal particles can be performed in the same manner as the growth in the preparation of seed crystal particles described above.

Further, the effect of the present invention becomes more remarkable when an oxidizing agent, particularly a compound represented by the above general formula [A], [B] or [C] is used.

The oxidizing agent for silver used in the method for preparing a seed crystal emulsion of the present invention refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely minute silver atoms, which are a by-product in the process of forming silver halide grains, into silver ions is effective. The silver ion generated here may form a poorly soluble silver salt such as silver halide, silver sulfide or silver selenide, or may form a readily soluble silver salt such as silver nitrate. May be.

The oxidizing agent for silver may be an inorganic material or an organic material.

As an example of the oxidizing agent, Japanese Patent Laid-Open No. 61-313 can be used.
4 and 61-3136, examples of the inorganic oxidant include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O,
2NaCO ₃ / 3H ₂ O ₂ , Na ₄ P ₂ O ₇ / 2H ₂ O
_{2, 2Na 2 SO 4 · H} 2 O 2 · 2H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2 O 6, K 2 P
₂ O ₈ ), a peroxy complex compound (for example, K ₂ [Ti
(O ₂ ) C ₂ O ₄ ] ・ 3H ₂ O, 4K ₂ SO ₄・ Ti
(O ₂ ) OH ・ SO ₄・ 2H ₂ O, Na ₃ [VO
_{(O 2) (C 2 H} 4) 2 · 6H 2 O), permanganate (e.g., KMnO _4), chromates (e.g., K ₂ C
r ₂ O ₇ ), oxyacid salts such as r ₂ O ₇ ), halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate) salts of high valent metals (eg potassium hexacyanoferrate) ) And thiosulfonate.

As organic oxidants, 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).

The preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents such as thiosulfonates, and organic oxidizing agents such as quinones.

A more preferred oxidizing agent is thiosulfonate, which can be selected from the compounds represented by the above-mentioned compounds [A], [B] and [C].

In the method for preparing a seed crystal emulsion of the present invention, at least one of the oxidizing agents for silver is added during the preparation process. The term "during the preparation step" may basically mean any step, but a particularly preferable method is a method of adding it during grain formation. Further, a method of adding after the desalting water washing step is also preferable.

It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for grain formation. Further, an oxidizing agent for silver may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. In addition, it is also preferable to add it several times in accordance with the formation of particles or continuously add it for a long time.

The addition amount of the oxidizing agent to silver is preferably 10 ^-7 to 10 ^-1 mol per mol of silver halide, and 10 ^-6.
To 10 ^-2 mol is more preferable, and 10 ^-5 to 10 ^-3 mol is most preferable.

In order to add the oxidizing agent for silver during the step of preparing the seed crystal emulsion, a method usually used for adding an additive to a photographic emulsion can be applied. Specifically, the water-soluble compound is an aqueous solution having a suitable concentration, and the water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, for example, alcohols, glycols, ketones, esters, Among the amides and the like, they can be dissolved in a solvent that does not adversely affect the photographic characteristics and added as a solution.

The thiosulfonic acid compounds represented by the above general formulas [A], [B] and [C] will be described in more detail.
When R, R ¹ and R ² are aliphatic groups, they are saturated or unsaturated, linear, branched or cyclic, aliphatic hydrocarbon groups, preferably alkyl groups having 1 to 22 carbon atoms, Is 2
To 22 alkenyl groups and alkynyl groups, which may be further substituted.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl,
t-butyl is mentioned.

Examples of the alkenyl group include allyl and butenyl. Examples of the alkynyl group include propargyl and butynyl.

When R, R ¹ and R ² are aromatic groups,
Included are monocyclic or fused ring aromatic groups. An aromatic group having 6 to 20 carbon atoms is preferable, and examples thereof include phenyl and naphthyl. These may be further substituted.

When R, R ¹ and R ² are heterocyclic groups, they have at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium and have at least 1 carbon atom.
It has a 3- to 15-membered ring. Preferably 3
A 6-membered heterocycle, for example, pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole. , Tetrazole, oxadiazole and thiadiazole.

Substituents for R, R ¹ and R ² include, for example, alkyl groups (eg, methyl, ethyl, hexyl),
Alkoxy group (eg, methoxy, ethoxy, octyl), aryl group (eg, phenyl, naphthyl, tolyl), hydroxy group, halogen atom (eg, fluorine,
Chlorine, bromine, iodine), aryloxy group (eg, phenoxy), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, butyryl,
Valeryl), sulfonyl group (for example, methylsulfonyl, phenylsulfonyl), acylamino group (for example,
Acetylamino, benzoylamino), sulfonylamino groups (eg methanesulfonylamino, benzenesulfonylamino), acyloxy groups (eg acetoxy,
Benzoxy), carboxyl group, cyano group, sulfo group,
Amino group, -SO ₂ SM group, (M is a monovalent shows a cation) -SO ₂ R ¹ group (R ¹ is the same) and the like.

As the divalent linking group represented by L,
An atom or atomic group containing at least one selected from C, N, S and O can be mentioned. As a concrete example,
Alkylene group, alkenylene group, alkynylene group, arylene group, -O-, -S-, -NH-, -CO-, -S.
O ₂ − and the like may be used alone or in combination.

L is preferably a divalent aliphatic group or a divalent aromatic group. When L is a divalent aliphatic group, specific examples thereof include the following groups and xylylene groups.

[0036]

[Chemical 3]

When L is a divalent aromatic group, specific examples thereof include a phenylene group and a naphthylene group.

These substituents may be further substituted with the above-mentioned substituents.

M is preferably a metal ion or an organic cation. Examples of the metal ion include lithium ion, sodium ion and potassium ion. Examples of organic cations include ammonium ions (for example, ammonium, tetramethylammonium,
Tetrabutylammonium), phosphonium ions (eg, tetraphenylphosphonium), and guanidyl groups.

When the general formula [A], [B] or [C] is a polymer, examples of its repeating unit include the following.

[0041]

[Chemical 4]

These polymers may be homopolymers or copolymers with other copolymerizable monomers.

The compounds represented by the general formula [A], [B] or [C] are described in JP-A-54-1019; British Patent 972, 211;
Journal of Organic Chemis
try (Journal of Organic Chemistry) 53, 396 (1988) and Chemica.
l Abstracts (Chemical Abstracts)
It can be easily synthesized by the method described or cited in Volume 59, 9776e.

The most preferable compound for the present invention is the compound represented by the general formula [A].

Specific examples of the compound represented by the general formula [A], [B] or [C] are shown below, but the invention is not limited thereto.

[0046]

[Chemical 5]

[0047]

[Chemical 6]

[0048]

[Chemical 7]

[0049]

[Chemical 8]

[0050]

[Chemical 9]

[0051]

[Chemical 10]

[0052]

[Chemical 11]

[0053]

[Chemical 12]

[0054]

[Chemical 13]

[0055]

[Chemical 14]

In the present invention, the seed crystal emulsion described above is used,
An internal latent image type direct positive silver halide emulsion is prepared, and the finally completed emulsion will be described below. In the present invention, silver halide grains having various shapes can be used. As an example, those having a regular crystal form such as a cube, octahedron, tetradecahedron and rhombic dodecahedron, and those having an irregular crystal form such as a sphere and a plate, One having the following plane ((hk1) plane), or a mixture of grains of these crystal forms can be mentioned. For particles with higher order, see the Journal of Imaging Science,
Reference can be made to pages 247 to 254 of Volume 30 (1986). The silver halide grains used in the present invention, even if they are normal crystals that do not contain twin planes, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photography (Corona Publishing Co.), p. 163, for example, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected and used from multiple twins and the like according to the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected if necessary. In the case of normal crystals, a cube consisting of (100) plane,
Octahedron consisting of (111) plane, Japanese Examined Patent Publication No. 55-42737
And JP-A-60-222842 (1)
It is possible to use dodecahedral grains having a 10) plane.
Furthermore, Journal of Imaging Science, Volume 30, 24
(H1) plane particles typified by (211), (hh1) plane particles typified by (331), and (210) plane typified as reported in 1986 (page 7).
Although the (hk1) plane particles represented by the (0) plane grains and the (321) plane are required to be devised in the preparation method, they can be selected and used according to the purpose. Tetrahedral grains in which (110) plane and (111) plane coexist in one grain, (100) plane and (110) plane
Particles whose faces coexist, or (111) faces and (110) faces
Particles in which two surfaces or a large number of surfaces coexist, such as particles in which surfaces coexist, can be selected and used according to the purpose.

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

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

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

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

The grain size of the emulsion used in the present invention depends on the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and grain thickness, or the sphere equivalent diameter of the volume by the Coulter counter method. Can be evaluated. It can be selected from ultrafine particles having a sphere-equivalent diameter of 0.05 μm or less and coarse particles having a diameter of more than 10 μm. Particles of 0.1 μm or more and 3 μm or less are preferable. The grain size distribution of the silver halide grains is arbitrary, but may be monodisperse. Here, monodisperse means
It is defined as a dispersion system in which 95% of the total weight or the total number of silver halide grains contained therein falls within ± 60% of the number average grain size, preferably within 40%.
Here, the number average grain size is the number average diameter of the projected area diameters of silver halide grains. Monodisperse emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748. These monodisperse emulsions are mixed and used. May be.

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

The present invention can obtain more remarkable effects when preparing tabular silver halide grains. The shape of tabular grains can be selected from triangles, hexagons, circles, and the like.
A regular hexagon with approximately six sides of equal length, as described in U.S. Pat. No. 4,996,137, is a preferred form. In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. Particles containing no dislocation lines, particles containing several dislocations, or particles containing many dislocations can be selected according to the purpose. It is also possible to select dislocations or curved dislocations that are introduced linearly with respect to a specific direction of the crystal orientation of the particles, or to introduce the dislocations throughout the particles or only at specific sites of the particles, for example, The dislocation can be introduced only in the fringe portion of the grain. Dislocation lines can be introduced not only in the case of tabular grains but also in the case of regular grains or amorphous grains typified by potato grains. For example, JP-A-63-220238 and JP-A-1-201649 disclose tabular silver halide grains in which dislocations are intentionally introduced.

In the tabular emulsion of the present invention, silver halide grains having an aspect ratio (circular equivalent diameter of silver halide grains / grain thickness) of 2 or more and 100 or less account for 50% (area) of all silver halide grains in the emulsion. An emulsion that exists above. An emulsion in which silver halide grains having an aspect ratio of 5 or more, and more preferably 5 to 8 are present in an amount of 50% (area) or more of all silver halide grains in the emulsion, is preferable.
The emulsion is preferably 70% or more, and particularly preferably 85% or more. Here, the equivalent circle diameter in a tabular silver halide grain is the equivalent circle diameter of two opposing parallel or nearly parallel principal planes (diameter of a circle having the same projected area as the principal plane), grain thickness. Represents the distance between the principal planes. When the aspect ratio exceeds 100, in the process until the emulsion is completed as a coated product,
There is a problem that the emulsion may be deformed or destroyed, which is not preferable.

The average grain diameter (corresponding to a circle) of tabular grains is 0.
3 μm or more, preferably 0.3 to 10 μm, more preferably 0.5 to 5.0 μm, and further preferably 0.5 to
It is 3.0 μm. The particle thickness is less than 1.5 μm, preferably 0.05 to 1.0 μm. Further, an emulsion having a grain thickness variation coefficient of 30% or less and high thickness uniformity is also preferable. Further, grains described in JP-A-63-163451, in which the grain thickness and the interplanar distance between twin planes are defined, are also preferable. The grain diameter and grain thickness of tabular grains can be measured by electron micrographs of grains as described in US Pat. No. 4,434,226.

Further, in the present invention, the tabular grains are preferably monodisperse. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-151618.

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

The silver halide grains used in the present invention are
Research Disclosure (RD) No. 17643
(Dec. 1978), pp. 22-23, "I. Emulsion preparation and types", and ibid. 1
8716 (November 1979), p. 648, ibid. Thirty
7105 (Nov. 1989), pages 863-865, and "Graphics and Chemistry" by Graphide, published by P.Glafkides Chimie et Pysique Photograhique,
Paul Montel, 1967), "Photographic emulsion chemistry" by Duffin, published by Focal Press (GFDuffin, Photograph
ic Emulsion Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VLZelikman et al, Making and Coating Pho
Tographic Emulsion, Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.
The method for producing the tabular silver halide grains and the technique for using the same have already been described, but Gatov, Photographic Sanenz & Engineering (Guto
ff, Photographic Science and Engineering), 14th
Volume 248-257 (1970); U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
It can be easily prepared by the methods described in 33,048, 4,439,520 and British Patent 2,112,157.

The silver halide emulsion comprising the above regular grains can be obtained by controlling the pAg and pH during grain formation. For more information, for example,
Sanence and Engineering (Photographic
Science and Engineering), Volume 6, 159-165
Page (1962); Journal of Photographic Science,
12: 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,7.
48. For monodisperse emulsions,
JP-A-48-8600, 51-39027 and 5
No. 1-83097, No. 53-137133, No. 54-
No. 48521, No. 54-99419, No. 58-376.
No. 35, No. 58-49938, Japanese Patent Publication No. 47-1138
6, U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748.

It is also possible to provide the seed crystal emulsion as silver halide for grain growth. In this case, it is preferable to add an emulsion having a small grain size. As an addition method, the whole amount can be added at once, divided into a plurality of times, or added continuously. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

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

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

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

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

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

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

The internal latent image type silver halide grains used in the present invention preferably have a core / shell structure as described above. The shell manufacturing method is disclosed in JP-A-63-151618.
No. 3,206,316, 3,317,322, 3,761,276, 4,269,927, 3,367,778 and the like. Can be In this case, the core / shell molar ratio (weight molar ratio) is preferably 1/30 to 5/1, more preferably 1/20 to 2/1, and further preferably 1/2.
It is 0 to 1/1.

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

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

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

Further, the sensitizing method using the oxidizing agent described above can also be applied. The oxidizing agent species, usage, etc. can be the same as those already described. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It is possible to select and use the method of performing reduction sensitization after using an oxidizing agent, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

It is advantageous to use gelatin as the protective colloid used when the emulsion of the present invention is prepared, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, A variety of synthetic hydrophilic polymeric substances such as a single or copolymer such as polyvinylpyrazole can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Photo.Japan, No.
16, an enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. Although many impurity ions are contained in gelatin, it is also preferable to use gelatin in which the amount of inorganic impurity ions is reduced by ion exchange treatment. Particularly, the Ca content is 100 ppm or less, preferably
A preferable result can be obtained by using the ion-exchanged gelatin so that the concentration becomes 30 ppm or less.

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

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

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

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. (For example, U.S. Pat. Nos. 3,615,613, 3,
615, 641, No. 3,617, 295, No. 3, 6
35,721, 2,933,390, 3,74
3,510, those described in JP-A-63-23145, etc.). The sensitizing dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,969.
JP-A-58-113928 discloses that spectral sensitization is carried out simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 58-113928. As described above, the chemical sensitization can be carried out prior to the chemical sensitization, or the spectral sensitization can be started by adding the silver halide grains before the completion of precipitation formation. Furthermore, US Pat. No. 4,2
Adding these said compounds separately, as taught in US Pat. No. 25,666, ie adding some of these compounds prior to chemical sensitization and the rest after chemical sensitization. Is also possible, and US Pat.
It may be at any time during the formation of silver halide grains, including the method disclosed in Japanese Patent No. 756.

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

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

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

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

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

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

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

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

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

[0096]

[Chemical 15]

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

[0098]

[Chemical 16]

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

[0100]

[Chemical 17]

The details are described in US Pat. Nos. 3,719,489 and 4,098,783. On the other hand, specific examples of the dye represented by the above general formula DYE are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. , 383, 4,195,992, 4,148,641, 4,148,643, 4,336,322: JP-A-51-114930.
56-71072: Research Disclosure 1763.
No. 0 (1978) and No. 16475 (1977). Examples of magenta dyes: U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308, and 3,954. , 476, 4,233,237, 4,255,509, 4,250,246, 4,142,891, 4,207,104, 4,287,292. Issue: JP-A-52-106,727
No. 53, No. 53, 628, No. 55-36, 804
No. 56-73,057, No. 56-71060,
Those described in No. 55-134. Examples of cyan dyes: US Pat. Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220 and 4,242. , 435, 4,142,891, 4,195,994, 4,147,544, 4,148,642; British Patent 1,551,138.
Nos. 54-99431 and 52-8827.
No. 53-47823, No. 53-143323, No. 5
4-99431, 56-71061; European Patents (EP) 53,037, 53,040; Rese
those described in arch Disclosure 17,630 (1978) and 16,475 (1977). These compounds are disclosed in JP-A-62-215,272, 1
It can be dispersed by the method described on pages 44 to 146. Further, these dispersions include those disclosed in JP-A-62-215,272.
No. 137-144 may be included.

(2) Silver Halide Emulsion In the present invention, various internal latent image type direct positive silver halide emulsions can be used in combination with the aforementioned internal latent image type direct positive silver halide emulsion of the present invention. .

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

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

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

F) Release Layer In the present invention, a release layer may be provided, if necessary, for peeling off the photosensitive sheet in the unit at any place after processing. Therefore, this peeling layer must be easy to peel off after the treatment. As a material for this, for example,
JP-A-47-8237, JP-A-59-220727, JP-A-59-229555, JP-A-49-4653, US Pat. Nos. 3,220,835, 4,359,518, and JP-A-49-4334. No. 56, No. 56-65133, No. 45
-24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 4,401,746, 4,366,227 and the like can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. For example, hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose,
And so on. Another example is various natural polymers such as alginic acid, pectin, and gum arabic.
Also various modified gelatins such as acetylated gelatin,
Phthalated gelatin is also used. Yet another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethylmethacrylate, polybutylmethacrylate, or a copolymer thereof may be used. The release layer can be a single layer,
Further, for example, JP-A-59-220727 and JP-A-60-6.
It may be composed of a plurality of layers as described in No. 0642.

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

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

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

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

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

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

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

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

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

[0116]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. Example-1 First, a method for preparing a silver halide emulsion will be described. The following 12 kinds of silver halide emulsions (Emulsion-A1 to A3, B, C, D1 to D3, E,
F, G, H) were prepared.

Preparation of Emulsion-A1 (octahedral internal latent image type direct positive emulsion): 0.05M potassium bromide, 1 g of 3,6-dithia-1,8-octanediol, 0.05 mg of lead acetate
And deionized gelatin with Ca content of 100ppm or less
The temperature was adjusted to 7 in 1000 mL of an aqueous gelatin solution containing g.
While keeping the temperature at 5 ° C, 0.4M silver nitrate aqueous solution and 0.4M potassium bromide aqueous solution are controlled by the control double jet method while controlling the addition rate of the potassium bromide aqueous solution so that the pBr becomes 1.60, and the silver nitrate aqueous solution 300mL Was added over 40 minutes. When the addition was completed, octahedral silver bromide crystals (hereinafter referred to as core particles) having a uniform particle size with an average particle size (equivalent sphere diameter) of about 0.7 μm were produced. Next, 1 mg of sodium thiosulfate, 90 mg of potassium tetrachloroaurate and 1.2 g of potassium bromide were added to this prepared solution in 1000 mL of water.
Chemical sensitization treatment was carried out by adding 3 mL of an aqueous solution dissolved in and heating at 75 ° C. for 80 minutes. After 0.15M potassium bromide was added to the emulsion solution chemically sensitized in this way, 0.9M silver nitrate aqueous solution and 0.9M silver nitrate aqueous solution were added while maintaining the temperature at 75 ° C as in the case of preparing core particles. Control solution of potassium bromide in pBr
670 mL of silver nitrate aqueous solution was added over 70 minutes while controlling the addition rate of the potassium bromide aqueous solution so that the ratio became 1.30. This emulsion was washed with water by a conventional flocculation method, and the above-mentioned gelatin, 2-phenoxyethanol, and methyl P-hydroxybenzoate were added to obtain an average particle size (equivalent sphere diameter) of about 1.4 μm. Further, octahedral silver bromide crystals (hereinafter referred to as internal latent image type core / shell grains) were obtained. Next, 100 mg of sodium thiosulfate and 40 parts of sodium tetraborate were added to this internal latent image type core / shell emulsion.
3 mL of an aqueous solution prepared by dissolving mg in 1000 mL of water was added, and further 14 mg of poly (N-vinylpyrrolidone) was added,
After ripening by heating at 0 ° C., an octahedral internal latent image type direct positive emulsion was prepared by adding 0.005 M potassium bromide.

Preparation of Emulsion-A2 (octahedral internal latent image type direct positive emulsion): In the preparation method of Emulsion-A1, the core grain preparation step is the core seed crystal Emulsion-E (mean equivalent spherical diameter is about 0). .7μ
An octahedral internal latent image type direct positive emulsion was prepared by the same preparation method as that for Emulsion-A1 except that it was omitted by using an octahedral silver bromide emulsion having a uniform grain size. In particular,
Distilled water was added to the core seed crystal emulsion-E containing 0.12 M silver bromide to adjust the total volume to 1600 mL, and then the temperature was adjusted to 75
The temperature was raised to 0 ° C., 1 g of 3,6-dithia-1,8-octanediol and 0.05 mg of lead acetate were added, and potassium bromide was further added to adjust pBr to 1.60.
Subsequent chemical sensitization and the like were the same as those for Emulsion-A1.

Preparation of Emulsion-A3 (octahedral internal latent image type direct positive emulsion): Emulsion-A2 except that core seed crystal emulsion-E is replaced with core seed crystal emulsion-F in the preparation method of A2.
An octahedral internal latent image type direct positive emulsion was prepared by the same preparation method as A2.

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

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

Emulsion-D1 (Hexagonal tabular internal latent image type direct positive emulsion) Preparation: 0.013 M potassium bromide and 320 mL of an aqueous gelatin solution containing 0.7% by weight of gelatin having an average molecular weight of 100,000 or less as described above. A 1.4 M silver nitrate aqueous solution containing gelatin and a 2 M potassium bromide aqueous solution were simultaneously mixed with each other by the double jet method for 1 minute while vigorously stirring. During this period, the gelatin aqueous solution was kept at 30 ° C.
Furthermore, after adding 80 mL of a gelatin solution containing 10% by weight of deionized gelatin having a Ca content of 100 ppm or less, 75 ° C.
The temperature was raised to. Then, 11 mL of 0.9 M silver nitrate aqueous solution was added over 3 minutes, 25% by weight ammonia aqueous solution was added, and aging was performed at 75 ° C. After completion of the aging, after neutralizing ammonia, 1.3 mg of lead acetate (added in an aqueous solution) was added, and a 1 M silver nitrate aqueous solution and a 1 M potassium bromide aqueous solution were used while accelerating the flow rate while maintaining pBr at 2.2 (end. The flow rate at that time was 6 times the flow rate at the start) and the addition was carried out by the double jet method. (The amount of the aqueous silver nitrate solution used was 133 mL.) The hexagonal tabular core particles obtained had an average projected area circle-equivalent diameter of 0.9 μm and an average thickness of 0.20 μm, which was 95% of the total projected area. Were occupied by hexagonal tabular grains. Then, add 0.11 M potassium bromide to the above emulsion suspension.
And 40 g of deionized gelatin, distilled water was added to adjust the total volume to 1300 mL, and the temperature was raised to 75 ° C.
0.3 g of 3,6-dithia-1,8-octanediol,
Sodium benzenethiosulfate 10 mg, potassium tetrachloroaurate 90 mg and potassium bromide 1.2 g are added to water 1000 mL.
Then, 2.4 mL of an aqueous solution dissolved in and 15 mg of lead acetate (added as an aqueous solution) were added, and the mixture was heated at 75 ° C. for 180 minutes for chemical sensitization. Next, the outer shell
Formation. In the same manner as in the preparation of the core particles, the 2M silver nitrate aqueous solution and the 2.5M potassium bromide aqueous solution were added to the thus chemically sensitized core particles so that the pBr would be 2.2. While controlling the amount and the addition rate, the addition was carried out by the double jet method at an accelerated flow rate (the flow rate at the end was 3 times the flow rate at the start). (The amount of the aqueous silver nitrate solution used was 810 mL.) After adding 0.3 M potassium bromide, this emulsion was washed with water by a conventional flocculation method and gelatin was added. Thus, a hexagonal tabular internal latent image type core / shell emulsion was obtained. The obtained hexagonal tabular grains have an average projected area circle equivalent diameter of 2.5 μm and an average thickness of 0.37 μm.
88% of the total projected area with an average volume size of 1.4 (μm) ³
Were occupied by hexagonal tabular grains. Next, 100 mg of sodium thiosulfate and 40 mg of sodium tetraborate were added to 10 parts of water in the hexagonal tabular internal latent image type core / shell emulsion.
A hexagonal tabular internal latent image type direct positive emulsion was prepared by adding 15 mL of an aqueous solution dissolved in 00 mL, and further adding 20 mg of poly (N-vinylpyrrolidone) and chemically sensitizing the grain surface by heating at 60 ° C. for 100 minutes. Was prepared.

Preparation of Emulsion-D2 (Hexagonal tabular internal latent image type direct positive emulsion): In the preparation method of Emulsion-D1, the step of preparing core grains was carried out by core seed crystal emulsion-G (mean projected area circle equivalent diameter 0.9 μm, average grain thickness 0.20 μm, and 95% of the total projected area was occupied by hexagonal tabular grains.) Internal latent image type direct positive emulsion was prepared. Specifically, to 300 g of core seed crystal emulsion-G, 1300 mL of water, 0.11 M of potassium bromide and 40 g of deionized gelatin were added, and the temperature was raised to 75 ° C, followed by the chemical preparation by the same preparation method as that of emulsion-D1. After the processing, the hexagonal tabular internal latent image type direct positive emulsion was prepared.

Emulsion-D3 (Hexagonal tabular internal latent image type direct positive emulsion) Preparation: Emulsion-D2 except that core seed crystal emulsion-G is replaced with core seed crystal emulsion-H.
A hexagonal tabular internal latent image type direct positive emulsion was prepared by the same preparation method as D2.

Emulsion-E (octahedral core seed crystal emulsion) preparation: 0.05M potassium bromide, 1 g of 3,6-dithia-1,8-octanediol, 0.05 mg of lead acetate and 1 of Ca content.
In 1000 mL of gelatin aqueous solution containing 60 g of deionized gelatin of 00 ppm or less, 0.7 M silver nitrate aqueous solution and 0.7 M potassium bromide aqueous solution were controlled while maintaining the temperature at 75 ° C. and the pBr was 1.6 by the control double jet method.
830 mL of an aqueous silver nitrate solution was added over 40 minutes while adjusting the addition rate of the aqueous potassium bromide solution so that the solution became 0. Next, wash with water by the conventional flocculation method,
Gelatin, 2-phenoxyethanol and methyl P-hydroxybenzoate were added to prepare 750 g of an octahedral core seed crystal emulsion. The obtained octahedral core seed crystal emulsion grains were octahedral silver bromide crystals (hereinafter referred to as core grains) having a uniform grain size with an average grain size (sphere equivalent diameter) of about 0.7 μm.

Preparation of Emulsion-F (octahedral core seed crystal emulsion): In the preparation method of Emulsion-E, after adding methyl P-hydroxybenzoate, 0.4 mg of compound 1-16 was added, and the mixture was added at 40 ° C. at 40 ° C. An octahedral core seed crystal emulsion was obtained by heating for a minute.

Emulsion-G (hexagonal tabular core seed crystal emulsion) preparation: 0.05 M of potassium bromide and 1.2 liter of an aqueous gelatin solution containing 0.7% by weight of gelatin having an average molecular weight of 100,000 or less as described above. A 1.4 M silver nitrate aqueous solution containing gelatin and a 2 M potassium bromide aqueous solution were vigorously stirred, and 33 mL of each was simultaneously mixed by the double jet method for 1 minute. During this period, the gelatin aqueous solution was kept at 30 ° C. Furthermore,
After adding 300 mL of a gelatin solution containing 10% by weight of deionized gelatin having a Ca content of 100 ppm or less, the temperature was raised to 75 ° C. Next, 40 mL of 0.9 M silver nitrate aqueous solution was added over 3 minutes, 25% by weight ammonia aqueous solution was added, and aging was performed at 75 ° C. After aging, neutralize the ammonia and add 5 mg of lead acetate (added as an aqueous solution).
MBr silver nitrate solution and 1M potassium bromide solution were added to pBr.
Was increased to 2.2 by the double jet method at an accelerated flow rate (the flow rate at the end was 6 times the flow rate at the start). (The amount of the aqueous solution of silver nitrate used was 500 mL.) Next, water was washed by a conventional flocculation method, and gelatin, 2-phenoxyethanol and methyl P-hydroxybenzoate were added, and 750 g of a hexagonal tabular core was added. A seed crystal emulsion was obtained. The obtained hexagonal tabular core seed crystal emulsion grains had an average projected area circle equivalent diameter of 0.9 μm and an average thickness of 0.
Hexagonal tabular grains accounted for 95% of the total projected area.

Preparation of emulsion-H (hexagonal tabular core seed crystal emulsion): In the preparation method of emulsion-G, after adding methyl P-hydroxybenzoate, 0.4 mg of compound 1-16 was added and 5
A hexagonal tabular core seed crystal emulsion was obtained by heating at 0 ° C. for 40 minutes.

Emulsions-A1, A were prepared according to the above-mentioned emulsion preparation method.
2, A3, and Emulsion-D1, D2, and D3 were prepared 20 times each, and Emulsion-A1-1 to Emulsion-A1-20 and Emulsion-A2-1 to Emulsion-A2-2 were prepared.
0, emulsion-A3-1 to emulsion-A3-20, emulsion-D1-1 to emulsion-D1-20, emulsion-D2-1 to emulsion-D2-20, emulsion-D3-1
~ Emulsion-D3-20 was prepared. Emulsion using a seed crystal emulsion-A2, A3, and emulsion-For D2 and D3, seed crystal emulsion-
Each of E, F, G, and H was prepared 6 times, and necessary amounts were collected from any preparation batch and used. Using these emulsions,
Comparative photosensitive element (Sample 10) having the structure shown in Table 1 below.
1) was created.

[0130]

[Table 1]

[0131]

[Table 2]

[0132]

[Table 3]

[0133]

[Table 4]

[0134]

[Table 5]

[0135]

[Table 6]

[0136]

[Table 7]

[0137]

[Chemical 18]

[0138]

[Chemical 19]

[0139]

[Chemical 20]

[0140]

[Chemical 21]

[0141]

[Chemical formula 22]

Next, the emulsions of the eighth layer, the fifteenth layer, and the twenty-second layer were sequentially replaced by Emulsion-A1-2 to Emulsion-A1-20 to prepare Samples 102 to 120 and Emulsion-A2-1 to Emulsion-. Samples 121 to 140, Emulsion-A3-1 to Emulsion-
Samples 141-160, emulsion-D1 replaced sequentially with A3-20
-1 to Emulsion-D1-20 to replace Samples 161 to 18
0, Emulsion-D2-1 to Emulsion-D2-20 were sequentially replaced to prepare Samples 181 to 200, and Emulsion-D3-1 to Emulsion-D3-20 were sequentially replaced to prepare Samples 201 to 220. (However, the emulsion was replaced at the same time with the same emulsion in all of the eighth layer, the fifteenth layer and the twenty-second layer.)
20 is Emulsion-A1, Samples 121 to 140 are Emulsion-A2,
Samples 141 to 160 are Emulsion-A3, Samples 161 to 180
Represents the degree of reproducibility when emulsion-D1 was prepared, Samples 181 to 200 were prepared from emulsion-D2, and Samples 201 to 220 were prepared from emulsion-D3. Table 2 shows the sample configuration.

[0143]

[Table 8]

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

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

The light-sensitive elements 101 to 220 are exposed from the emulsion layer side through a continuous wedge of gray, and then overlapped with the cover sheet, and the processing solution is put between both materials so as to have a thickness of 75 μm. Deployed using. The exposure was adjusted for 1/100 ″ by adjusting the exposure illuminance so that the exposure amount was constant. The treatment was performed at 25 ° C., and after 10 minutes, the transfer density was measured with a color densitometer to determine the maximum density and the minimum density. The density and sensitivity were evaluated.
The minimum concentration and sensitivity were defined as follows. That is, the logarithmic value of the reciprocal of the exposure amount is displayed on the horizontal axis and each color density is displayed on the vertical axis, and a characteristic curve is drawn. The maximum density is the color density in the unexposed area, the minimum density is the color density in the area where the exposure amount is sufficiently high, and the logarithm of the reciprocal of the exposure amount E that gives (maximum density + minimum density) / 2 (= Log1 / The relative value of E) to the reference sample (Sample 101) was defined as the sensitivity. Next, regarding the maximum concentration, the minimum concentration, and the sensitivity, samples 101 to 120, samples 121 to 140,
Samples 141-160, Samples 161-180, Sample 181
The average value and the standard deviation were calculated for each of 20 samples of 200 to 200 and samples 201 to 220. The results are shown in Table-3 and Table-4.

[0147]

[Table 9]

[0148]

[Table 10]

Samples 121 to 140 and Sample 141 of the present invention
.About.160, Samples 181 to 200, and Samples 201 to 220 have small standard deviations of maximum density, minimum density, and sensitivity, and the prepared emulsion-A2, emulsion-A3, emulsion-D2, and emulsion-D3 have reproducible reproducibility. I know it's good. In particular, Emulsion-A3 and Emulsion-D3 prepared by using a core seed crystal emulsion containing Compound 1-16 which is a typical example of the compounds represented by the formulas [A], [B] and [C] of the present invention are Samples 141 to 16 used
0, Samples 201 to 220 show that the effect is remarkable.

Example 2 Sample No. 1 of Example-1 of JP-A-2-90145 was prepared in the same manner as in the preparation of a comparative photosensitive element (Sample 101).
The emulsion of the fourth layer, the seventh layer, and the twelfth layer of No. 1 was changed to Emulsion-A1-
1-Emulsion-A1-20, Emulsion-A2-1 to Emulsion-A2-
20, Emulsion-A3-1 to Emulsion-A3-20, Emulsion-D1
-1-Emulsion-D1-20, Emulsion-D2-1-Emulsion-D2
-20, Emulsion-D3-1 to Emulsion-D3-20 were replaced, and the same experiment was conducted. The results were the same as in Example-1, and the effect of the present invention was confirmed.

Example 3 Sample N of Example-1 of JP-A-3-189643 was prepared in the same manner as in the preparation of a comparative photosensitive element (Sample 101).
o. 106 emulsions of the third, fifth and ninth layers were replaced with emulsion-
A1-1 to Emulsion-A1-20, Emulsion-A2-1 to Emulsion-
A2-20, emulsion-A3-1 to emulsion-A3-20, emulsion-D1-1 to emulsion-D1-20, emulsion-D2-1 to emulsion-D2-20, emulsion-D3-1 to emulsion-D3- A similar experiment was performed by substituting 20. The results were the same as in Example-1, and the effect of the present invention was confirmed.

Example 4 Samples 101 to 220 produced in Example-1 were processed into a form that could be loaded into an instant camera according to the procedure of Japanese Utility Model Laid-Open No. 63-150939, and then photographed using the camera. The same experiment as in Example-1 was performed by the method. The results were the same as in Example-1, and the effect of the present invention was confirmed.

[0153]

INDUSTRIAL APPLICABILITY According to the present invention, an internal latent image type direct positive silver halide emulsion having good preparation and reproducibility, and a color diffusion transfer light-sensitive material using this emulsion with little fluctuation in sensitivity and S / N can be obtained. I understood it.

Claims (5)

[Claims] 1. An internal latent image type direct positive silver halide emulsion prepared by using a seed crystal emulsion prepared through a desalting step. 2. All tabular silver halide grains having an average grain diameter of 0.3 μm or more and an aspect ratio (equivalent circle diameter of silver halide grain / grain thickness) of 2 or more and 100 or less prepared through a desalting step. An aspect ratio (equivalent circle diameter of silver halide grain / grain thickness) of 2 or more and 100 or less prepared by using a silver halide emulsion characterized by containing 50% or more of silver halide grains as a seed crystal emulsion. An internal latent image type direct positive silver halide emulsion containing certain tabular silver halide grains in an amount of 50% or more of all silver halide grains. 3. The internal latent image type direct positive silver halide emulsion according to claim 1, wherein the seed crystal emulsion contains at least one oxidizing agent for silver. Silver emulsion. 4. The internal latent image type direct positive silver halide emulsion according to claim 3, wherein the oxidizing agent is represented by the following general formula [A],
An internal latent image type direct positive silver halide emulsion, which is a compound selected from the compounds represented by [B] and [C]. [Chemical 1] In the formula, R, R ¹ and R ² may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compound represented by the general formula [A], [B] or [C] is a polymer containing a divalent group derived from the structure represented by [A], [B] or [C] as a repeating unit. Good. If possible, R, R ¹ , R ² , L
May combine with each other to form a ring. 5. A support having at least one photosensitive silver halide emulsion layer in combination with a dye image-forming substance, which dye-forming substance is represented by the following general formula [I]:
A color diffusion transfer light-sensitive material comprising a non-diffusible compound which releases a diffusible dye or a precursor thereof in association with silver development, or a compound which changes its own diffusivity, wherein at least one silver halide emulsion layer is formed. 5. A color diffusion transfer light-sensitive material containing at least one internal latent image type direct positive silver halide emulsion according to claim 1. General formula [I] (DYE-Y) _n -Z {DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like structure. To produce a difference in the diffusivity of the compound represented by (DYE-Y) _n -Z corresponding to or opposite to the photosensitive silver salt having a latent image, or to release DYE and release the DYE. And (DYE-Y) _n -Z represent a group having a property of causing a difference in diffusibility, n represents 1 or 2, and when n is 2, two DYE-Y are the same. But it can be different. }