JPH0659376A - Internal latent image type direct positive silver halide emulsion and color diffusion transfer photosensitive material using same - Google Patents

Abstract

PURPOSE:To provide the internal latent image type direct positive silver halide emulsion high in sensitivity and large in the difference between maximum density and minimum density and the color diffusion transfer photosensitive material using it. CONSTITUTION:The internal latent image type direct positive silver halide emulsion is characterized by using a polymer having repeating units each derived from an ethylenically unsaturated monomer having at least one kinds of thioether structure as a deflocculator to form silver halide and adding at least one metal selected from Mn, Cr, Cu, Zn, Cd, Pb, Bi, and Re, and the metals of group VIII of the periodic table. The color diffusion transfer photosensitive material is characterized by having at least one photosensitive silver halide emulsion layer containing a combination of this emulsion and a dye image- forming substance represented by the formula: (DYE-Y)n-Z in which DYE is a dye group or a dye precursor group; Y is a simple bond or a bonding group; Z is a group for controlling diffusivity of this compound; and (n) is 1 or 2.

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 is superior in sensitivity and gradation characteristics to 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. 3,761,27.
No. 6, and Japanese Patent Publication No. 60-55821, using an internal latent image type direct positive silver halide photographic emulsion,
When developing a silver halide grain having an internal latent image formed thereon with a surface developing solution (a developing solution which leaves the latent image forming site inside the silver halide grain substantially undeveloped), a uniform exposure is given or a nucleating agent is added. By using it, a positive image is obtained.

Gelatin has been used for a long time as a peptizer for silver halide photographic emulsions for use in image formation. The main reasons are that the protective colloid property is large, and secondly the sol-gel conversion is easy and easy to handle, and coating is possible. However, gelatin is easily decomposed by bacteria and fungi, and the quality of gelatin varies because it comes from the living body. For these problems, it is already known to use synthetic polymers as peptizers in place of gelatin, and polymers having repeating units derived from ethylenically unsaturated monomers containing at least one thioether structure. It is also known to use as a peptizer. For example, U.S. Pat. No. 3,615,62
No. 4, No. 3,536, 677, No. 3,692, 753
Issue No. 3,690,888 Issue 3,679,425
Issue No. 3,706,564 Issue No. 3,706,565
Issue No. 3,713,833 Issue 3,840,628
, And 4,400,463, and research
Disclosure, Vol. 104, pp. 44-48 and Journal of Imaging Science (Journal
of Imaging Science), Volume 31, 148-156. Although the above-mentioned patents and literatures describe examples of direct positive emulsions, these prior arts are direct-positive emulsions which have been previously covered, and provide uniform exposure or use a nucleating agent. No mention is made of an internal latent image type direct positive emulsion which forms a positive image by.

It is possible to sensitize a silver halide emulsion by adding a transition metal compound at several stages of producing the silver halide emulsion in US Pat. No. 2,448,06.
No. 0. It is known that there is a significant difference in the photographic effect of the transition metal compound in the silver halide emulsion between the case where the transition metal compound is added during the formation of the silver halide grains and the case where it is added after the precipitation of the silver halide grains. There is. The former case is called a metal dopant. About these, Research Disclosure, Volume 176 (December 1978)
Issue monthly) item 17643.

In an internal latent image type direct positive silver halide photographic emulsion, it is known that the low density portion on the reversal characteristic curve becomes harder by doping with metal ions. This is described, for example, in U.S. Pat.
No. 367,778, No. 3,447,927, No. 3,5
31,291, 3,761,267, 3,76
1,276, 3,850,637, 3,92
No. 3,513, No. 4,035,185, No. 4,44
4,874, 4,444,865, 4,43
No. 3,047, No. 4,395,478, British Patent Nos. 1,151,782, No. 1,529,011, and JP-A-1-145647. However, the low-concentration portion on the reversal characteristic curve by doping with metal ions is not at a sufficiently satisfactory level,
In addition, the drawback is that the maximum density is lowered. In addition, these patents do not describe the definition of metal ion ligands or their effects.

On the other hand, European Patent No. 0,336,425,
U.S. Pat. And a silver halide emulsion having excellent gradation gradation stability and improved low illumination failure. Here, it is recognized that the hexacoordinated transition metal complex is accommodated in the void space of a single halide ion inside the crystal structure,
This is different from the conventional belief that transition metals are incorporated into silver halide grains as single ions or atoms. However, this patent limits the types of transition metals to rhenium, ruthenium, osmium and iridium, and does not describe cobalt. Further, it does not describe an internal latent image type direct positive silver halide agent.

Further, JP-A-2-259749 discloses an internal latent image type direct positive silver halide emulsion containing a hexacyanoiron complex among iron complexes, which has a high maximum density and a low minimum density, and has a reversal negative in a high illuminance exposure. It is described that a direct positive silver halide photographic light-sensitive material with less image formation can be obtained, but the central metal is limited to iron, and manganese, chromium, rhenium, ruthenium, osmium, iridium and cobalt are described. No, and only gelatin is described as a deflocculant.
Further, in the internal latent image type direct positive emulsion, it is particularly desired that the difference between the maximum density and the minimum density is large.
No. 749 was still insufficient in this respect.

In US Pat. No. 3,690,888, an inverted image having excellent discriminating property is obtained by a method for producing silver halide grains which occlude polyvalent metal ions in the presence of a peptizer composed of an acrylic polymer. Although it is described that it can be obtained, this patent does not describe the definition of the ligand of the metal ion or the effect thereof.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an internal latent image type direct positive silver halide emulsion having high sensitivity and a large difference between the maximum density and the minimum density, and a color diffusion transfer light-sensitive material using the same. It is to be.

[0010]

An object of the present invention is to provide an internal latent image type direct positive silver halide emulsion described in (1), (2), (3) and (4) below and a color using the same. Achieved by diffusion transfer photosensitive material. (1) A silver halide emulsion grain is formed by using a polymer having a repeating unit derived from an ethylenically unsaturated monomer having at least one thioether structure in its side chain as a peptizer, and the halogenation is carried out. An internal latent image type direct positive electrode characterized by adding at least one metal selected from manganese, chromium, copper, zinc, cadmium, lead, bismuth, rhenium, and Group 8 metal of the periodic table to the silver emulsion grain formation. Silver halide emulsion. (2) The internal latent image type direct positive silver halide emulsion as described in (1) above, wherein the added metal is a hexacoordinate cyano complex represented by the following general formula (I). General formula (I) [M (CN) ₆ ] ^n-In formula (I), M is Ir, Co, Ru, Os, Re, F.
represents e, Mn or Cr, and n represents 3 or 4. (3) The internal latent image type direct positive silver halide emulsion as described in (1) above, wherein the added metal is lead. (4) A silver developing layer having at least one photosensitive silver halide emulsion layer in combination with a dye image-forming substance, which dye is represented by the following general formula (II). In a color diffusion transfer light-sensitive material comprising a non-diffusible compound which releases a diffusible dye or a precursor thereof, or a compound whose diffusivity itself changes, at least one of the silver halide emulsion layers comprises A color diffusion transfer light-sensitive material comprising the internal latent image type direct positive silver halide emulsion described in any one of 1) to (3) above. Formula (II) (DYE-Y) _n -Z {DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, 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 constitution of the present invention will be described in detail below. The polymer having at least one thioether structure in the side chain used as the peptizer in the present invention will be described below. Preferred examples of the polymer containing at least one thioether structure of the present invention include repeating units derived from an ethylenically unsaturated monomer having a thioether structure in the side chain, represented by the following general formula [A]. Examples of the polymer include

[0012]

[Chemical 1]

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and L ₁ represents -CON.
(R ² )-(R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group having 1 to 6 carbon atoms),-
COO-, -NHCO-, -OCO-,

[0014]

[Chemical 2]

(R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, or a substituted or unsubstituted alkyl group, alkoxy group, acyloxy group or aryloxy group),

[0016]

[Chemical 3]

(R ² , R ³ and R ⁴ are the same as above). L ₂ represents a linking group connecting L ₁ and R, i represents 0 or 1, j represents 1 or 2, and R represents a monovalent substituent. ) The linking group represented by L ₂ is specifically

[0018]

[Chemical 4]

It is represented by

J ¹ , J ² , J ³ , and J ⁴ may be the same or different, and --CO--, --SO _2- , --CON.
(R ⁵ )-(R ⁵ is a hydrogen atom, an alkyl group (having 1 to
6) or a substituted alkyl group (having 1 to 6 carbon atoms). ), —SO ₂ N (R ⁵ ) — (R ⁵ has the same meaning as above),
^{-N (R 5) -R 6 -} (R 5 is as defined above, R ⁶ is an alkylene group having 1 to 4 carbon ^{atoms), - N (R 5)} -R 6 -N
(R ⁷ )-(R ⁵ and R ⁶ are as defined above, R ⁷ represents a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms) or a substituted alkyl group (having 1 to 6 carbon atoms)), -O-. , -S-, -N
^{(R 5) -CO-N (} R 7) - (R 5, R 7 are as defined ^{above), - N (R 5)} -SO 2 -N (R 7) - (R 5, R
⁷ is as defined above, -COO-, -OCO-, -N (R
⁵⁾ CO ₂ - (R ⁵ is as defined ^{above), - N (R 5)} CO
-(R < ⁵ > is synonymous with the above) etc. can be mentioned.
X ¹ , X ² , X ³ and X ⁴ may be the same or different, and an alkylene group, a substituted alkylene group, an arylene group,
It represents a substituted arylene group, an aralkylene group, or a substituted aralkylene group. p, q, and r represent 0 or 1. However, p, q, and r never become 0 at the same time. Also, L
² contains at least one thioether structure. In the above, X ¹ , X ² , X ³ and X ⁴ may be the same or different from each other and represent an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or a phenylene group, and an alkylene group. May be linear or branched. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene,
Tetramethylene, pentamethylene, hexamethylene, decylmethylene and the like, aralkylene groups such as benzylidene and substituted or unsubstituted phenylene groups such as p-phenylene, m-phenylene and methylphenylene.

The substituent of the alkylene group, aralkylene group or phenylene group represented by X ¹ , X ² , X ³ and X ⁴ is a halogen atom, a nitro group, a cyano group, an alkyl group, a substituted alkyl group or an alkoxy group. , A substituted alkoxy group, a group represented by —NHCOR ⁸ (R ⁸ represents an alkyl, a substituted alkyl, phenyl, a substituted phenyl, an aralkyl, a substituted aralkyl group), —NHSO ₂ R
⁸ (R ⁸ is as defined above), —SOR ⁸ (R ⁸ is as defined above), —SO ₂ R ⁸ (R ⁸ is as defined above), —COR ⁸
(R ⁸ is as defined above),

[0022]

[Chemical 5]

A group represented by (R ⁹ and R ¹⁰ may be the same or different from each other and represent a hydrogen atom, alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl or substituted aralkyl group),

[0024]

[Chemical 6]

Examples thereof include a group represented by (R ⁹ and R ¹⁰ have the same meanings as described above), an amino group (which may be substituted with an alkyl group), a hydroxyl group or a group which is hydrolyzed to form a hydroxyl group. When there are two or more substituents, they may be the same or different.

Further, examples of the substituent of the above-mentioned substituted alkyl group, substituted alkoxy group, substituted phenyl group and substituted aralkyl group include a hydroxyl group, a nitro group, an alkoxy group having 1 to about 4 carbon atoms, -NHSO ₂ R ⁸ ( R ⁸ is as defined above, -N
Group represented by HcOR ⁸ (R ⁸ is as defined above), the formula 5, group represented by Formula ^{_{6, -SO 2 R 8 (R}} 8 is as defined above), - COR ⁸ (R ⁸ is as defined above ), A halogen atom, a cyano group, an amino group (which may be substituted with alkyl) and the like.

R represents a monovalent substituent, specifically, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. As the alkyl group, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-
Butyl, n-hexyl, n-octyl, n-dodecyl and the like can be mentioned. In addition, as the substituent of the alkyl group and the aryl group, a halogen atom, a nitro group, a cyano group, an alkyl group, a substituted alkyl group, an alkoxy group can be used in the same manner as described above for X ¹ , X ² , X ³ and X ^4. Group, a substituted alkoxy group, a group represented by -NHCOR ⁸ (R ⁸ is alkyl,
Substituted alkyl, phenyl, substituted phenyl, aralkyl,
Represents a substituted aralkyl group), -NHSO ₂ R ⁸ (R ⁸
Is as defined above, -SOR ⁸ (R ⁸ is as defined above),
SO ₂ R ⁸ (R ⁸ has the same meaning as above), —COR ⁸ (R ⁸ has the same meaning as above), the groups represented by Chemical Formulas 5 and 6 above, an amino group (which may be substituted with an alkyl group), Examples thereof include a hydroxyl group and a group that is hydrolyzed to form a hydroxyl group.

Next, typical examples of the ethylenically unsaturated monomer which gives the repeating unit represented by the general formula [A] will be listed below. 3-thiapentyl acrylate 2-thiabutyl acrylate 3-thiapentyl methacrylate 2-thiabutyl methacrylate N- (3-thiapentyl) acrylamide N- (3-thiabutyl) acrylamide N- (3-thiapentyl) methacrylamide 5-thiaheptyl acrylate N- (7-thiaheptyl) acrylamide N- (3-thiaoctyl) acrylamide N- (7-thianonyl) acrylamide N- (2,5-dimethyl-4-thiahexyl) methacrylamide N-acryloylmethionine N-methacryloylmethionine N- acryloyl methionine methyl ester N-(3,6-dithiaheptyl) acrylamide N-[2,2-bis (1-thiapropyl) ethyl] acrylamide _{CH 2 = CH-COOCH 2 CH} 2 OCOCH 2 CH 2 COOCH 2 CH 2 SCH ₂ CH ₃

[0029]

[Chemical 7]

[0030] 3-thiapentyl-4-vinyl benzoate _{CH 2 = CH-CONHCH 2 COOCH} 2 CH 2 SCH 2 CH 3 CH 2 = CH-CONH (CH 2) 3 COOCH 2 CH 2 SCH 2 CH 3

The polymer having a repeating unit represented by the general formula [A] in the present invention is preferably water-soluble, and if necessary, other ethylenically unsaturated monomer may be copolymerized. Particularly preferred copolymerizable ethylenically unsaturated monomers are those whose homopolymers are water, acidic aqueous solution, or alkaline aqueous solution,
Specifically, nonionic monomers such as acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-acryloylmorpholine, N-ethylacrylamide, N-vinylpyrrolidone, etc.

[0032]

[Chemical 8]

[0033]

[Chemical 9]

A monomer having an anionic group such as
The salt (for example, Na, K salt, ammonium salt, etc.), N, N-diethylaminoethyl methacrylate, N, N
-Dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N- (N, N-dimethylaminopropyl) acrylamide, N- (N, N-dihexylaminomethyl) acrylamide, 3- (4-pyridyl) propyl acrylate, Tertiary amines such as N, N-diethylaminomethylstyrene, or salts thereof (eg hydrochloride, sulfate, acetate) or N, N, N-trimethyl-N-vinylbenzylammonium chloride,
Mention may be made of monomers having a cationic group such as quaternary ammonium compounds such as N, N, N-trimethyl-N- (3-acrylamidopropyl) ammonium chloride. Among these, nonionic monomers and monomers having anionic functional groups are particularly preferable. Further, in the polymer having the repeating unit represented by the general formula [A], other ethylenically unsaturated monomers can be copolymerized within a range that does not impair the water solubility. Examples of such a monomer include ethylene, propylene, 1-butene, isobutene, styrene, α-methylstyrene, vinyl ketone, monoethylenically unsaturated ester of fatty acid (eg vinyl acetate, allyl acetate), ethylenically unsaturated Esters of monocarboxylic or dicarboxylic acids (eg methylmethacrylate, ethylmethacrylate, n
-Butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate), monoethylenically unsaturated compounds (eg acrylonitrile) or dienes (eg butadiene, isoprene) Etc. can be mentioned.

In the polymer containing a repeating unit represented by the general formula [A] of the present invention, the ratio of the monomer containing a thioether group varies depending on the monomer structure, purpose of use, etc., and is generally 0. The range is 0.1 to 100% by weight, and particularly preferably 1 to 70% by weight. Specific examples of the polymer having a repeating unit represented by the general formula [A] of the present invention are shown below, but the present invention is not limited thereto. P-1 3-thiapentyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (1/1 molar ratio) P-2 3-thiapentyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid sodium Copolymer (1/2 mole ratio) P-3 3-thiapentyl acrylate / 2-acrylamido-2-methylpropane sodium sulfonate copolymer (1/3 mole ratio) P-4 3-Thiapentyl acrylate / 2-Acrylamido-2-methylpropanesulfonic acid sodium copolymer (1 / 4.5 molar ratio) P-5 3-thiapentyl acrylate / 2-acrylamido-2-methylpropane sodium sulfonic acid copolymer (1 / 6 mol ratio) P-6 3-thiapentyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid Copolymer (1/9 mole ratio) P-7 3-thiapentyl methacrylate / 2-acrylamido-2-methylpropane sodium sulfonate copolymer (1/1 mole ratio) P-8 3-thiapentyl Methacrylate / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (1/6 molar ratio) P-9 2-thiabutylacrylamide / 2-acrylamido-2-methylpropane sodium sulfonic acid copolymer (1 / 6 mol ratio) P-10 3-thiapentyl acrylate / acrylic acid /
Sodium acrylate copolymer (1/3/3 molar ratio) P-11 3-thiapentyl acrylate / acrylamide copolymer (1 / 12.5 molar ratio) P-12 N- (3-thiapentyl) acrylamide / acrylamide / Sodium acrylate copolymer (1/1/2
Molar ratio) P-13 2-thiabutyl acrylate / methyl methacrylate / 2-acrylamido-2-methylpropane sulfonic acid sodium copolymer (1/1/5 molar ratio) P-14 N- (3-thiabutyl) acrylamide / Sodium acrylate / sodium styrene sulfonate copolymer (1
/ 4/4 molar ratio) P-15 3-thiapentyl acrylate / methyl acrylate / N, N-dimethylaminoprohyl methacrylamide sulphate copolymer (1/3/4 molar ratio) P-16 3-thiapentyl- 4-vinyl benzoate /
N, N-dimethylaminomethylstyrene sulfate copolymer (1/5 molar ratio) P-17 N-acryloylmethionine Na salt / methyl methacrylate / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (1 / 5/5 molar ratio) P-18 N-acryloylmethionine methyl ester /
2-Acrylamido-2-methylpropanesulfonic acid sodium copolymer (1/6 molar ratio) P-19 N- (3,6-dithiaheptyl) acrylamide / acrylamide / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer Combined (1/5/6 molar ratio) P-20 N- [2,2-bis (1-thiapropyl) ethyl] acrylamide / N-vinylpyrrolidone / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer ( (1 / 0.25 / 8 molar ratio)

The above-mentioned thioether structure-containing monomers and polymers are described in, for example, US Pat. No. 3,536,677.
No. 3,615,624, No. 3,679,425
No. 3, No. 3,692,753, No. 3,706,564
Issue, Research Disclosu
re) 104, pp. 44-48 (1972) and the like, and the synthetic method thereof can also be carried out according to the above-mentioned literature.

The polymer of the present invention can be produced by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization and bulk polymerization. The method of initiating polymerization includes a method using a radical initiator, a method of irradiating light or radiation, a thermal polymerization method, and the like. These polymerization methods and methods for initiating the polymerization are described in, for example, Sadaji Tsuruta "Polymer Synthesis Reaction", revised edition (published by Nikkan Kogyo Shimbun, 1971). Among the above-mentioned polymerization methods, the solution polymerization method using a radical initiator is particularly preferable. The solvent used in the solution polymerization method is water or, for example, ethyl acetate, methanol, ethanol, 1-propanol, 2-propanol, acetone, dioxane, N,
Various organic solvents such as N-dimethylformamide, N, N-dimethylacetamide, toluene, n-hexane, and acetonitrile may be used alone or as a mixture of two or more kinds, or as a mixed solvent with water.

The polymerization temperature must be set in relation to the molecular weight of the polymer to be produced, the kind of the initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but usually 30 ° C. to 100 ° C.
Polymerize in the range of ° C. Examples of the radical initiator used for the polymerization include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2-amidino). Azo initiators such as propane) dihydrochloride, 4,4'-azobis (4-cyano-pentanoic acid), and peroxide initiators such as benzoyl peroxide and potassium persulfate are preferable.

The deflocculating agent having a thioether as a functional group of the present invention is used in the formation of silver halide grains, and the method used is as follows: it is dissolved in a halide salt solution or a silver salt solution for forming silver halide grains. The solution can be added to the reaction vessel, or can be added in parallel with the silver salt solution. Preferably, it is added as an aqueous solution in the reaction vessel in advance. The amount used is not particularly limited, but is 0.1 per mol of silver halide.
~ 150 g, preferably 0.5-80 g. In the present invention, grain formation of silver halide grains-washing with water, desalting-
It is preferable not to use gelatin in the chemical sensitization step, but gelatin may be used if necessary. It is also possible to add 30 g or more, and preferably 50 g or more per mol of silver halide by using gelatin as a binder after the emulsion preparation and before coating. For usable binders, see Research Disclosure, Volume 176, Item 1
The description of 7643 can be referred to.

In the present invention, since the temperature at the time of particle formation does not cause sol-gel conversion of the polymer, particles can be formed sufficiently even at 0 ° C. or below unless solidified, and there is no protein such as gelatin that solidifies at high temperature. Although it can be sufficiently used at a temperature of not less than 0 ° C, it is preferably used in the range of 5 ° C to 95 ° C.

The metal dopant added during the formation of silver halide grains will be described below. In the present invention, during the formation of silver halide emulsion grains, manganese, chromium, copper, zinc, cadmium, lead, bismuth, rhenium,
And at least one metal selected from Group 8 metals of the periodic table. The metal used in the present invention can be added in the form of a salt that can be dissolved at the time of grain formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydroxide salt or hexacoordinate complex salt, and tetracoordinate complex salt. .

The added metal is preferably a hexacoordinate cyano complex represented by the following general formula (I). General formula (I) [M (CN) ₆ ] ^n-In formula (I), M is Ir, Co, Ru, Os, Re, F.
represents e, Mn or Cr, and n represents 3 or 4. As the counterion of the hexacoordinate cyano complex used in the present invention, alkali metal ions such as potassium and sodium are preferably used.

In another preferred embodiment, the added metal is lead. In this case, lead is preferably used as lead acetate [Pb (CH ₃ COO) ₂ ].

The amount of the metal used in the present invention is preferably 10 ^-10 mol or more and 10 ^-4 mol or less per mol of silver halide, and 1.0 × 10 ^-8 per mol of silver halide. It is more preferable that the amount is not less than 10 mol and not more than 10 ⁻⁴ mol.

The metal used in the present invention may be added and contained at the time of preparation of silver halide grains, that is, at any stage before and after nucleation, growth, physical ripening and chemical sensitization. The pAg of these metals when added during the preparation of silver halide grains is 6
It is preferably 11 or less.

The metal used in the present invention is preferably added after being dissolved in water or a suitable solvent. Alkali halides (eg KCl, NaCl, K to stabilize the solution)
Br, NaBr, etc.) can be used. Moreover, you may add alkali etc. as needed.

The metal used in the present invention may be added directly to the reaction solution during the formation of silver halide grains, or may be added to an aqueous solution of halide for forming silver halide grains, an aqueous solution of silver salt, or other solution. It is preferable to add the particles by adding them to form particles. It is also preferable to combine various addition methods.

The hydrogen ion concentration in the reaction solution when the metal used in the present invention is added is preferably pH = 1 or higher, more preferably pH = 3 or higher.

The metal used in the present invention can be used in combination with other metal ions. Other metals include Mg and C
a, Sr, Ba, Al, Sc, Y, La, Ga, Au,
Hg, Tl, In, Sn, etc. can be used. 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.

The present invention is applicable 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 when imagewise exposed, a latent image is mainly formed inside the silver halide grains. With a silver halide emulsion,
Specifically, a certain amount of a silver halide emulsion is coated on a transparent support and exposed to light for a fixed time of 0.01 to 1 second, and the following developer A (“internal type” developer) is used. Inside,
The maximum density obtained when developed at 20 ° C. for 5 minutes was the same as the above.
It is defined as having a density which is at least 5 times greater than the maximum density obtained when developed in ("surface type" developer) at 20 ° C for 5 minutes. 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 metaborate 35 g potassium bromide 1 g Water added 1 liter As an internal latent image type silver halide emulsion, for example, US Pat. 456,953 and 2,592,250 and the like, conversion type silver halide emulsions, and the first phase and the first phase as described in U.S. Pat. No. 3,935,014 and the like. Laminated structure silver halide emulsions having different two-phase halogen composition, doped with metal ions, or Such core / shell type silver halide emulsion coated with shell academic sensitized core particles. 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.
Examples thereof include US Pat.
317,322, 3,761,266, 3,7
61,276, 3,850,637, 3,92
No. 3,513, No. 4,035,185, No. 4,18
4,878, 4,395,478, 4,50
4,570, JP-A-57-136641, JP-A 61-
No. 3137, No. 63-151618, JP-A No. 1-13
Examples thereof include those described in No. 1547.

In order to directly obtain a positive image, a uniform second exposure is applied to the entire surface of the photosensitive layer after the above-mentioned internal latent image type silver halide emulsion is imagewise exposed and before or during the development processing ("light Fogging method ", for example, British Patent 1,151,363
No.) or in the presence of a nucleating agent (“chemical fogging method”, for example, Research Disclosure, Volume 151, No. 151).
62, pp. 76-78), but a method of directly obtaining a positive image by the "chemical fogging method" is preferred in the present invention. The nucleating agent used in the present invention will be described later. As described above, in order to directly obtain a positive image using the internal latent image type silver halide emulsion, after the image exposure, before the development processing or during the development processing, the entire surface is uniformly exposed to the second exposure, or It is obtained by carrying out development processing in the presence of a nucleating agent. As a nucleating agent, US Pat.
3,785, 2,588,982 hydrazines, U.S. Pat. No. 3,227,552 hydrazides, hydrazones, British Patent 1,283,
No. 835, JP-A Nos. 52-69613 and 55-138.
No. 742, No. 60-11837, No. 62-21045.
No. 1, 62-291637, U.S. Pat. No. 3,615,
No. 615, No. 3,719,494, No. 3,734,7
No. 38, No. 4,094,683, No. 4,115,12
No. 2, No. 4,306,016, No. 4,471, 044
Heterocyclic quaternary salt compounds described in U.S. Pat.
No. 4,430,92, a sensitizing dye having a substituent having a nucleating action in a dye molecule, described in US Pat.
No. 5, No. 4,031,127, No. 4,245, 037
No. 4,255,511, 4,266,013
No. 4,276,364, British Patent No. 2,012,4
No. 43, etc., and thiourea-bonded acylhydrazine compounds, and US Pat. Nos. 4,080,270 and 4,
Acylhydrazine compounds having a thioamide ring or a heterocyclic group such as triazole or tetrazole described in British Patent No. 278,748 and British Patent No. 2,011,391B as an adsorption group are used. The amount of the nucleating agent used here is preferably an amount which gives a sufficient maximum density when the internal latent image type emulsion is developed with a surface solid 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. About 0.1 mg to 5 per mole
A range of g is practically useful, preferably about 0.5 mg to about 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.

Various shapes of silver halide grains can be used in the present invention. 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, Examples thereof include those having the following plane ((hkl) plane), and a mixture of grains of these crystal forms. For particles with higher surfaces, see the Journal of Imaging Science.
247 of the maging Science magazine, Volume 30 (1986)
See pages 254. The silver halide grains used in the present invention, even if they are normal crystals that do not contain twin planes, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photography (Corona Publishing Co.), p. 163, for example, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected and used from multiple twins and the like according to the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected if necessary. In case of normal crystal (10
A cube consisting of (0) faces, an octahedron consisting of (111) faces,
JP-B-55-42737, JP-A-60-222842
The dodecahedral grains composed of (110) planes disclosed in Japanese Patent No. 3,095,049 can be used. Furthermore, Journal of Imaging Science, Vol. 30, p. 247, 198.
(Hll) plane particles typified by (211) and typified by (331) as reported in 2006 (hh1)
The face particles, the (hk0) face particles typified by the (210) face, and the (hk1) face particles typified by the (321) face may be selected and used according to the purpose although some preparation methods are required. Tetrahedral particles in which (110) plane and (111) plane coexist in one grain, particles in which (100) plane and (110) plane coexist, or particles in which (111) plane and (110) plane coexist. For example, particles in which two surfaces or a large number of surfaces coexist can be selected and used according to the purpose.

As the silver halide composition of these grains, any 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-57-154).
No. 232, No. 58-108533, No. 58-2484
69, 59-48755, 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 No. 1,027,146.
issue). 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 have 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 plane and the side surface 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 the 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, etc. can be used in combination, and they are used in different emulsion layers and / or the same emulsion layer. It is possible to

In the present invention, more preferable effects can be obtained when tabular silver halide grains are used. Regarding tabular silver halide grains, Cleve, Photography Theory and Practice has already been written by Cleve.
(1930)), 131; Gatov, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), 14th
Vol. 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 Nos. 59-99433, 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.
It is described in detail in the issue. 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. 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.

The ratio of the average grain diameter to the average grain thickness in tabular grains (hereinafter referred to as grain diameter / thickness) is preferably 2 or more, preferably 3 to 12, and particularly 5
It is preferably -8. Here, the average grain diameter of tabular silver halide grains is the average value of the diameters of circles of two opposing parallel or nearly parallel principal planes (the diameter of a circle having the same projected area as the principal plane). The average particle thickness represents the average value of the distances between the main planes. Here, the grain diameter / thickness can be obtained by averaging the grain diameters / thicknesses of all tabular grains. A simple method is to calculate the average diameter of all tabular grains and the average thickness of all tabular grains. It can also be calculated as a ratio.

The tabular grains have a diameter (corresponding to a circle) of 0.3 μm or more, preferably 0.3 to 10 μm, more preferably 0.
5 to 5.0 μm, more preferably 0.5 to 3.0 μm
Is. The grain thickness is less than 1.0 μm, preferably 0.0
It is 5 to 0.5 μm. Furthermore, the coefficient of variation of particle thickness is 3
Emulsions with high thickness uniformity of 0% or less are also preferable. Further, grains described in JP-A-63-163451, in which the grain thickness and the interplanar distance between twin planes are defined, are also preferable. In the present invention, the tabular grains account for 50% or more of the total grain projected area in the emulsion containing the tabular grains. It is preferably 70% or more, more preferably 90% or more. The grain diameter and grain thickness of tabular grains can be measured by US Pat.
It can be determined by electron micrographs of particles as described in the method described in No. 34,226.

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
US Pat.
Raffle particles described in 643,966 are examples.

The silver halide grains used in the present invention are
Research Disclosure (RD) No. 1764
3 (Dec. 1978), pp. 22-23, "I. Emulsion preparation and types", ibid. 1
8716 (November 1979), p. 648, ibid. Three
07105 (November 1989), pages 863-865,
And Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P. Glafkides, Chimie et Pysique Photograph
ique, Paul Montel, 1967), "Photographic emulsion chemistry" by Duffin, published by Focal Press (GF Duffin, Photog
raphic Emulsion Chemistry, Focal Press, 196
6), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et al, Making and
Coating Photographic Emulsion, Focal Press, 196
It can be prepared using the method described in 4) or 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, a combination thereof or the like. Good. Method of forming grains in the presence of excess silver ion (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. Also, tabular grains are described in Gatov, Photographic Science and Engineering (Guto
ff, Photographic Science and Engineering), 14th
Vol. 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 consisting of the above-mentioned regular grains can be obtained by controlling the pAg and pH during grain formation. For more information, for example,
Science and Engineering (Photographic S
cience and Engineering), Volume 6, 159-165 (1962); Journal of Photographic Science, 1
Volume 2, Pages 242-251 (1964), U.S. Pat. No. 3,
655,394 and British Patent 1,413,748.
No. Regarding monodisperse emulsions, JP-A Nos. 48-8600, 51-39027 and 51-
83097, 53-137133, and 54-48.
No. 521, No. 54-99419, No. 58-37635.
No. 58-49938, Japanese Patent Publication No. 47-11386
No. 3,655,394 and British Patent No. 1,413,748.

The method of adding pre-precipitated silver halide grains to a reaction vessel for preparing an emulsion is described in US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Is more preferable. These can be used as seed crystals, and are also effective when provided as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size. As an addition method, the whole amount can be added at once, divided into a plurality of times, or added continuously. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

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

In addition to 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 disclosed in US Pat. Nos. 2,996,287, 3,342,605 and 3,3.
The method can be selected from the methods described in 415,650, 3,785,777 and West German Laid-Open Patents 2,556,885, 2,555,364.

Silver halide solvents are useful for the purpose of promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Other ripening agents can also be used. The total amount of these ripening agents can be compounded in the dispersion medium in the reactor before adding silver and halide salts, and the halide salts, silver salts or peptizers can be added in the reactor as well. Can also be introduced. As another variation, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As the ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264.
Nos. 2,448,534 and 3,320,06
Instructions can be found in No. 9. Organic thioether compounds (for example, US Pat. Nos. 3,271,157 and 3,574,574)
No. 628, No. 3,737,313, No. 3,021,2
No. 15, No. 3,057,724, No. 3,038,80
5, No. 4,276,374, No. 4,297,439
No. 3,704,130, No. 4,782,130
JP-A-57-104926) and thione compounds (for example, JP-A-53-82408).
No. 55-77737, U.S. Pat. No. 4,221,8.
Tetrasubstituted thioureas described in JP-A No. 63-63, compounds described in JP-A-53-144319),
Examples thereof include mercapto compounds described in JP-A-57-202531, which can promote the growth of silver halide grains, and amine compounds (for example, JP-A-54-100717).

During the production of an emulsion containing tabular grains, a silver salt solution (eg AgN) added to accelerate grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the O ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferably used. Regarding these methods, for example, British Patent No. 1,335,925 and US Pat.
672,900, 3,650,757, 4,2
42,445, JP-A-55-142329 and JP-A-55.
The description of No. 158124 can be referred to.
The above silver halide solvent is effective for promoting the ripening.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be effective in some cases. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanate, carbonate,
Phosphate and acetate may be present. Regarding these, US Pat. Nos. 2,448,060 and 2,628,
No. 167, No. 3,737,313, No. 3,772,0
No. 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, Japanese Patent Publication No. 60-558
A polymer as described in No. 21 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 of
the Photographic Process, 4th ed., Macmillan, 197
7), pp. 67-76, using active gelatin, and Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, June 1975. ,
13452, U.S. Pat. Nos. 2,642,361 and 3,
297,466, 3,772,031, 3,8
57,711, 3,901,714, 4,26
6,018, and 3,904,415, and British Patent 1,315,755, p.
It can be carried out using Ag, 5 to 10, pH 5 to 8 and a temperature of 30 to 80 ° C., using sulfur, selenium, tellurium, gold, platinum, palladium, iridium, rhodium, osmium, rhenium or a combination of a plurality of these sensitizers.

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. The chemical sensitization aids used include compounds known to control fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine and azapyrimidine. 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 Duffin, "Photoemulsion Chemistry", pp. 138-143 (Focal Press, 1966).

Japanese Examined Japanese Patent Publication No. 58-1410, Mois
ar) et al., Journal of Photographic Science, 25, 1977, pp. 19-27, silver halide emulsions can reduce and sensitize the inside of grains during the precipitation 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, U.S. Pat. No. 2,518,698, and US Pat.
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 reduction sensitization, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. The chemical sensitization methods described in US Pat. Nos. 3,917,485 and 3,966,476 can also be applied.

Further, JP-A-61-3134 and 61-3
The sensitizing method using an oxidizing agent described in JP-A No. 136 can also be applied. The oxidizing agent for silver refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions is effective. The silver ions generated here may form a poorly soluble silver salt such as silver halide, silver sulfide and silver selenide, or may form a readily soluble silver salt such as silver nitrate. Good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Inorganic oxidizers include ozone, hydrogen peroxide and its adducts (eg Na
BO 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 salts (eg K ₂ S _{2
O 8, K 2 C 2 O} 6, K 2 P 2 O 8), peroxy complex compounds _{(e.g., 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, permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O ₇ ) and other oxyacid salts, halogen elements such as iodine and bromine, and perhalogenates (eg, periodic acid). Potassium), high valent metal salts (eg potassium hexacyanoferrate) and thiosulfonates. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B). ) Is mentioned as an example. Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonates and organic oxidizing agents of quinones. 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.

As the protective colloid used in the preparation of the emulsion of the present invention, it is advantageous to use a repeating unit represented by the general formula [A] and derived from an ethylenically unsaturated monomer having a thioether structure in its side chain. However, other hydrophilic colloids can be used together. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl. Various synthetic hydrophilic polymer substances such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. 1
6, the enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or an enzymatic hydrolyzate of gelatin may also be used. Although many impurity ions are contained in gelatin, it is also preferable to use gelatin in which the amount of inorganic impurity ions is reduced by ion exchange treatment.

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

In the present invention, spectral sensitization can be performed using a sensitizing dye. Examples of the sensitizing dye 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 thereof, 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, US Pat. Nos. 3,615,613 and 3,3
No. 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 can be performed 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 the addition before the completion of the silver halide grain precipitation formation. Furthermore, US Pat. No. 4,22
Adding these said compounds separately as taught in US Pat. No. 5,666, ie adding some of these compounds prior to chemical sensitization and the rest after chemical sensitization. Is also possible, and US Pat. No. 4,183,7
It may be at any time during the formation of silver halide grains including the method disclosed in No. 56.

The addition amount is 10 per 1 mol of silver halide.
It can be used in an amount of from ^-8 to 10 ^-2 mol, but about 5 x 10 ^-5 to 2 x 10 ^-3 mol is more effective for a more preferable silver halide grain size of 0.2 to 1.2 µm.

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,
No. 678, azoles 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. These additives are described in more detail in Research Disclosure Item 17643 (1978).
Year), the same Item 18716 (November 1979) and the same
It is described in Item 307105 (November 1989), and the relevant portions are summarized in the table below.

Types of Additives RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1989) 1 Chemical sensitizer page 23 648 page right column 866 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, pages 23 to 24, page 648, right column, page 866 to 868, supersensitizer, page 649, right column 4, whitening agent, page 24, page 647, page 868, 5 antifoggant, pages 24 to 25, page 649, right column 868 to 870 Stabilizer 6 Light absorber, 25 to 26 page 649 Right column, 873 Filter dye, ~ 650 page left column, UV absorber 7 Stain inhibitor 25 page, Right column 650 page, Left column 872 to right column 8 Dye image stabilizer page 25 page 650 left column page 872 9 hardener page 26 page 651 page left column 874 to 875 page 10 binder 26 page same as above 873 to 874 page 11 plasticizer and lubricant page 27 page 650 right column page 876 12 Coating aid, pages 26-27 ibid., 875-876 pages Surfactant 13 Antistatic agent, p. 27 ibid., Pages 876-877, 14 Matting agent, 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
No. 1 is described. As the mordant, a polymer mordant is preferable. The polymer mordant is a polymer having a secondary or tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation, or the like and having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. It is a thing. The amount of mordant applied is generally 0.5.
10 to 10 g / m ^2, preferably 1.0 to 5.0 g / m ^{2, and} particularly preferably ² to 4 g / m ² . As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and the like are used, and gelatin is preferable. In the image receiving layer, the anti-fading agents described in JP-A-62-30620, JP-A-62-30621 and JP-A-62-215272 can be incorporated. C) White reflective layer The white reflective layer forming the white background of the color image usually contains a white pigment and a hydrophilic binder. The white content for the white reflective layer includes barium sulfate, zinc oxide, barium stearate,
Silver flakes, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, titanium dioxide and the like are used. Further, non-film-forming polymer particles made of styrene or the like are also used. Further, these may be used alone or may be mixed and used within a range capable of obtaining a desired reflectance. A particularly useful white pigment is titanium dioxide. The whiteness of the white reflective layer is
Although it depends on the type of pigment, the mixing ratio of the pigment and the binder, and the coating amount of the pigment, the light reflectance is preferably 70% or more. Generally, the greater the amount of pigment applied, the better the whiteness, but as the imaging dye diffuses through this layer, the pigment resists the diffusion of the dye,
It is desirable to have an appropriate coating amount. Titanium dioxide 5
A white reflective layer having a light reflectance of 78 to 85% with light having a wavelength of 540 nm is preferred, which is applied to -40 g / m ² , preferably 10 to 25 g / m ² . Titanium dioxide can be selected from various commercially available brands and used. Among these, it is particularly preferable to use rutile type titanium dioxide. Most of the commercially available products are surface-treated with alumina, silica, zinc oxide or the like. In order to obtain a high reflectance, the surface treatment amount is preferably 5% or more. Examples of commercially available titanium dioxide include Ti-pure R93 manufactured by DuPont.
In addition to 1, there are those described in Research Disclosure No. 15162. As a binder for the white reflective layer, an alkali-permeable polymer matrix, for example, gelatin, polyvinyl alcohol, or a cellulose derivative such as hydroxyethyl cellulose or carboxymethyl cellulose can be used. A particularly preferred binder for the white reflective layer is gelatin. The ratio of white pigment to gelatin is
1/1 to 20/1 (weight ratio), preferably 5/1 to 10
It is / 1 (weight ratio). In the white reflective layer, Japanese Patent Publication Sho 62
It is preferable to incorporate an anti-fading agent such as -30620 and 62-30621.

D) Light-shielding layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the white reflective layer and the photosensitive layer. As the light shielding agent, any material having a light shielding function is used, but carbon black is preferably used. US Pat. No. 4,61
You may use the decomposable dye as described in 5,966.
The binder for coating the light-shielding agent may be any as long as it can disperse carbon black, and gelatin is preferable. Examples of carbon black raw materials include D
onnel Voet "Carbon Black" MarcelDekker, Inc. (1
Any method such as a channel method, a thermal method and a furnace method as described in 976) can be used. The particle size of carbon black is not particularly limited, but is preferably 90 to 1800Å. The addition amount of the black pigment as the light-shielding agent may be adjusted depending on the sensitivity of the light-sensitive material to be shielded, but it is preferably about 5 to 10 in optical density.

E) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming substance is provided above the light shielding layer. The constituent elements will be described below. (1) Dye image-forming substance The dye image-forming substance used in the present invention is a non-diffusible compound that releases a diffusible dye (may be a dye precursor) in association with the silver phenomenon, 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 (II). Formula (II) (DYE-Y) _n -Z {DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z represents an image-like structure. To produce a difference in the diffusivity of the compound represented by (DYE-Y) _n -Z corresponding to or opposite to the photosensitive silver salt having a latent image, or to release DYE and release the DYE. And (DYE-Y) _n -Z represent a group having a property of causing a difference in diffusibility, n represents 1 or 2, and when n is 2, two DYE-Y are the same. But it can be different. According to the function of Z, it is roughly classified into a negative type compound which becomes diffusive in the silver developed area and a positive type compound which becomes diffusible in the undeveloped area. Specific examples of the negative Z include those that are oxidized and cleaved to release a diffusible dye as a result of development. Specific examples of Z include U.S. Pat. Nos. 3,928,312, 3,993,638, 4,076,529, 4,152,153, 4,055,428 and 4,053. , 312, 4,198,235, 4,179,291, 4,149,892, 3,844,785, 3,443,943, 3,751,406. No. 3,443,939, No. 3,443,940, No. 3,628,952, No. 3,980,479, No. 4,183,753, No. 4,142,891, 4,278,750, 4,139,379, 4,218,368, 3,421,964, 4,199,355, 4,199,354, 4 , 135,929, 4,336,322, 4,139,389, HirakiAkira 53-50736 issue, same 51-104343 JP, same 54-130122 JP, the same 5
No. 3-110827, No. 56-12642, No. 56-
16131, 57-4043, 57-650.
No. 57-20735, No. 53-69033, No. 54-130927, No. 56-164342, No. 5
7-119345 and the like. Among Z of the negative type dye-releasing redox compound, a particularly preferable group is an N-substituted sulfamoyl group (as the N-substituent, 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.

[0091]

[Chemical 10]

For positive type compounds, Angevante Chemi Inst. Ed. Engl., 22, 191
(1982). A specific example thereof is a compound (dye developing agent) which is initially diffusible under alkaline conditions but is oxidized by development to become non-diffusible. Effective Z for this type of compound is described in US Pat.
Typical examples are those listed in No. 83,606. Further, as another type, a diffusible dye is released by self-ring closure under an alkaline condition, but the dye is substantially not released when oxidized by development. Specific examples of Z having such a function are described in US Pat. No. 3,980,479 and JP-A-53-69033.
No. 54-130927, U.S. Pat. No. 3,421,9.
64, 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 has been imagewise oxidized by silver development. Regarding the atomic group having such a function, for example, U.S. Pat. Nos. 4,183,753, 4,142,891, 4,278,750, 4,139,379, and 4,218 are disclosed. 368, JP-A-53-1108827,
U.S. Pat. Nos. 4,278,750 and 4,356,249.
No. 4,358,525, JP-A-53-11082.
No. 7, No. 54-130927, No. 56-164342
No., Open Technical Report 87-6199, European Patent Publication 220,
746A2 and the like. Specific examples thereof will be illustrated below, but the present invention is not limited thereto.

[0093]

[Chemical 11]

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.

[0095]

[Chemical 12]

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: US Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. , 383, 4,195,992, 4,148,641, 4,148,643, 4,336,322: JP-A-51-114930.
56-71072: Research Disclosure 1763.
No. 0 (1978) and No. 16475 (1977). Examples of magenta dyes: U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308 and 3,954. , 476, 4,233,237, 4,255,509, 4,250,246, 4,142,891, 4,207,104, 4,287,292. No .: JP-A-52-106727,
53-23628, 55-36804, 56
-73057, 56-71060, 55-13
What is described in No. 4. Examples of cyan dyes: US Pat. Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220 and 4,242. , 435, 4,142,891, 4,195,994, 4,147,544, 4,148,642; British Patent 1,551,138.
Nos. 54-99431 and 52-8827.
No. 53-47823, No. 53-143323, No. 5
4-99431, 56-71061; European Patents (EP) 53,037, 53,040; Rese
those described in arch Disclosure 17,630 (1978) and 16,475 (1977). These compounds are disclosed in JP-A-62-215272, 144.
It can be dispersed by the method described on page 146. Further, in these dispersions, JP-A-62-215272, 137
The compounds described on pages 144 to 144 may be included.

(2) Silver Halide Emulsion As the silver halide emulsion of the present invention, those described above are used.

(3) Construction of Photosensitive Layer For the reproduction of natural colors 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 install an intermediate layer. When the developer is used in combination with a non-diffusible dye image-forming substance, the intermediate layer preferably contains a non-diffusible reducing agent to prevent diffusion of the oxidized product of the developer. Specific examples thereof include non-diffusible hydroquinone, sulfonamide phenol, sulfonamide naphthol, and the like, and more specifically, JP-A-50-2.
1249, 50-23813, JP-A-49-10.
6329, 49-129535, U.S. Pat.
36,327, 2,360,290, 2,40
3,721, 2,544,640, 2,73
2,300, 2,782,659, 2,93
7,086, 3,637,393, 3,70
0,453, British Patent 557,750, JP-A-57.
No. 24941, No. 58-21249, and the like. Regarding the dispersion method thereof, JP-A-60-23
8831 and Japanese Examined Patent Publication No. 60-18978. When a compound capable of releasing a diffusible dye by silver ion as described in JP-B-55-7576 is used, it is preferable to include a compound for capturing silver ion in the intermediate layer. In the present invention, an irradiation prevention layer, a UV absorber layer, a protective layer and the like are coated as necessary.

F) Peeling Layer In the invention, a peeling layer may be provided for peeling off the photosensitive sheet in the unit at any place after processing, if necessary. Therefore, this peeling layer must be easy to peel off after the treatment. Materials for this purpose include, for example, JP-A-47-8237, JP-A-59-220727 and JP-A-5-220727.
9-229555, 49-4653, U.S. Pat. Nos. 3,220,835, 4,359,518, JP-A-49-4334, 56-65133, 45-.
24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 4,401,746 and 4,366,227 can be used. One of the specific examples is a water-soluble (or alkali-soluble) cellulose derivative. For example, hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. Another example is various natural polymers such as alginic acid, pectin, and gum arabic. Also, various modified gelatins such as acetylated gelatin and phthalated gelatin can be used. Yet another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethylmethacrylate, polybutylmethacrylate, or a copolymer thereof may be used. The release layer can be a single layer,
Further, for example, JP-A-59-220727 and JP-A-60-6.
It may be composed of a plurality of layers as described in No. 0642.

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 and neutralize the alkali after processing to stabilize the image. A transparent cover sheet having a layer) is used.

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

H) Layer Having Neutralizing Function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize an alkali carried from the treatment composition, and if necessary, Accordingly, it may have a multi-layered structure including layers such as a neutralization rate adjusting layer (timing layer) and an adhesion enhancing layer. A preferred acidic substance is a substance containing an acidic group having a pKa of 9 or less (or a precursor group which gives such an acidic group by hydrolysis), more preferably oleic acid described in US Pat. No. 2,983,606. Higher fatty acids such as US Pat. No. 3,362,819
Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides as disclosed in US Pat. No. 2,290,699; acrylic acid and acrylic acid as disclosed in French Patent 2,290,699 Ester isotopes;
No. 4,139,383 or Research Disclosure No. 16102 (19
Mention may be made of latex-type acidic polymers as disclosed in 77). Others, US Patent 4,08
No. 8,493, JP-A Nos. 52-153739 and 53-
No. 1023, No. 53-4540, No. 53-4541
The acidic substances disclosed in JP-A No. 53-4542 and the like can also be mentioned. Specific examples of acidic polymers include ethylene,
Examples thereof include copolymers of vinyl monomers such as vinyl acetate and vinyl methyl ether with maleic anhydride, and n-butyl esters thereof, copolymers of butyl acrylate and acrylic acid, cellulose, and acetate-hydrogenphthalate. The polymer acid can be used as a mixture with a hydrophilic polymer. As such a polymer,
Examples include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polymethyl vinyl ether and the like. Of these, polyvinyl alcohol is preferable. Further, the polymer acid is a polymer other than a hydrophilic polymer,
For example, cellulose acetate or the like may be mixed. The coating amount of the polymer acid is adjusted by the amount of alkali spread on the photosensitive element. The equivalent ratio of polymer acid and alkali per unit area is preferably 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stains are generated on the white background portion, and if it is too large, the hue is changed or the light resistance is deteriorated. A more preferable equivalent ratio is 1.0 to 1.3. If too much or too little hydrophilic polymer is mixed, the quality of the photograph will be degraded. The weight ratio of hydrophilic polymer to polymeric acid is 0.1 to 10, preferably 0.3 to 3.0. Additives can be incorporated into the layer having a neutralizing function of the present invention for various purposes. For example, hardening agents well known to those skilled in the art for hardening this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. for improving the brittleness of the film can be added. In addition, if necessary, an antioxidant, a fluorescent brightening agent, a development inhibitor and a precursor thereof may be added. Timing layers used in combination with the neutralization layer include polymers that reduce alkali permeability such as gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like; A latex polymer produced by copolymerizing a small amount of a hydrophilic comonomer such as an acrylic acid monomer to increase the activation energy of alkali permeation; a polymer having a lactone ring is useful. Among them, JP-A-54-136328,
US Pat. Nos. 4,267,262 and 4,009,030
No. 4,029,849, and other timing layers using cellulose acetate; JP-A-54-128
No. 335, No. 56-69629, No. 57-6843.
U.S. Pat. Nos. 4,056,394 and 4,061,4
No. 96, No. 4,199,362, No. 4,250,24
No. 3, No. 4,256,827, No. 4,268,604
Latex polymers prepared by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid; disclosed in U.S. Pat. No. 4,229,516; polymers having a lactone ring disclosed in U.S. Pat. No. 4,229,516; -25735
Nos. 56-97346, 57-6842, European Patent (EP) 31,957A1, 37,72.
The polymers disclosed in 4A1 and 48412A1 are particularly useful. In addition, those described in the following documents can also be used. US Pat. Nos. 3,421,893, 3,455,686, 3,575,701, 3,778,265, 3,785,815, 3,847,615, and US Pat. 4,088,493, 4,123,275, 4,148,653, 4,201,587, 4,288,523, 4,297,431, West German patent application (OLS) 1,6
22,936, 2,162,277, Research D
isclosure 15162, No. 151 (1976).
The timing layer using these materials may be used alone or in combination of two or more layers. In addition, a timing layer made of these materials can be used, for example, in US Pat.
029, West German patent application (OLS) 2,913,164
No. 3,014,672, JP-A-54-15583.
No. 7, 55-138745, and the like, development inhibitors and / or their precursors, hydroquinone precursors, and other useful photographic additives disclosed in US Pat. No. 4,201,578. It is also possible to incorporate the precursor etc.
Further, as a layer having a neutralizing function, JP-A-63-1
Providing an auxiliary neutralization layer as described in JP-A-68648 and JP-A-63-168649 is effective in reducing a change in transfer density with time after the treatment.

I) Others In addition to the layer having a neutralizing function, a back layer, a protective layer, a capture mordant layer, a filter dye layer and the like may be provided as a layer having an auxiliary function. The back layer is provided for adjusting curl and imparting slipperiness. Filter dyes may be added to this layer. The protective layer is mainly used to prevent adhesion to the back surface of the cover sheet and adhesion to the protective layer of the photosensitive material when the photosensitive material and the cover sheet are superposed. The 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 like the dye image-receiving layer described above, and is disclosed in JP-A-1-198747 and JP-A-2-1987.
No. 82253. 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 back layer, the protective layer, the capture mordant layer, or the like, or a single layer may be provided. .

III. Alkaline Processing Composition The processing composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element and placed on the back surface of the support or on the side of the photosensitive layer opposite to the processing liquid. It forms a pair with a light-shielding layer to completely shield the photosensitive layer from external light, and at the same time, develops the photosensitive layer with the components contained therein. Therefore, in the composition, an alkali, a thickener, a light-shielding agent, a developing agent, and further, a development accelerator for controlling the development, a development inhibitor, and an antioxidant for preventing the deterioration of the developing agent. Contains etc. A sunscreen is always included in the composition. Alkali is sufficient to adjust the pH of the liquid to 12 to 14, and alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide, lithium hydroxide), alkali metal phosphates (eg potassium phosphate). Examples thereof include guanidines and quaternary amine hydroxides (eg, tetramethylammonium hydroxide), but potassium hydroxide and sodium hydroxide are preferred. The thickener is necessary for uniformly developing the processing liquid and for maintaining the close contact between the photosensitive layer and the cover sheet. For example, an alkali metal salt of polyvinyl alcohol, hydroxyethyl cellulose or carboxymethyl cellulose is used, and preferably hydroxyethyl cellulose or sodium carboxymethyl cellulose is used. As the light-shielding agent, any dye or pigment, or a combination thereof, can be used as long as it does not diffuse to the dye image-receiving layer to generate stain. Carbon black is a typical example. As the preferred developing agent, any developing agent can be used as long as it cross-oxidizes the dye image-forming substance and does not substantially cause stain when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor type. These developers may be included in the appropriate layers of the light sensitive element or in the alkaline processing liquid. Specific examples of the compound include aminophenols and pyrazolidinones. Of these, pyrazolidinones are particularly preferable because they generate less stain. For example, 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3
-Pyrazolidinone, 1- (3'-methyl-phenyl)-
4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-
4-hydroxymethyl-3-pyrazolidinone, and the like. JP-A-62-215272 7 for either photosensitive sheet, cover sheet or alkaline processing composition
2-91, development accelerators, 146-155, hardeners, 201-210, surfactants 210
Fluorine-containing compounds described on page 222, thickeners described on pages 225 to 227, antistatic agents described on pages 227 to 230, 230
The polymer latex described on page 239 to the matting agent described on page 240 may be included.

[0105]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited thereto. Example-1 First, a method for preparing a silver halide emulsion will be described. Preparation of emulsion A-1 (internal latent image type direct positive emulsion): 13 g
Of potassium bromide and 0.05 g of 1,8-dihydrooxy-3,6-dithiaoctane in 1000 cc of an 8% by weight gelatin aqueous solution while maintaining the temperature at 75 ° C. and a 0.4 M silver nitrate aqueous solution and 0. A 4M aqueous solution of potassium bromide has a pBr of 1.30 by the control double jet method.
300 cc of silver nitrate aqueous solution was added over 40 minutes while controlling the addition rate of the potassium bromide aqueous solution such that When the addition is completed, the average particle diameter (sphere equivalent diameter) is about 0.
Octahedral silver bromide crystals with uniform grain size of 8 μm (hereinafter referred to as core grains) were produced. Next, to the silver bromide grains, 0.7 mg of sodium thiosulfate and 0.4 mg of potassium chloroaurate (both were added in an aqueous solution) were added, and the temperature was 75 ° C.
Chemical sensitization treatment was performed by heating at 80 ° C. for 80 minutes.
The chemical sensitized core particles were treated with 0.8 M silver nitrate aqueous solution and 0.8 M potassium bromide aqueous solution by the control double jet method while maintaining the temperature at 75 ° C. as in the core particle preparation. 740 cc of an aqueous silver nitrate solution was added over 60 minutes while adjusting the addition rate of the aqueous potassium bromide solution so that the ratio was 2.71. This emulsion was washed with water by a conventional flocculation method, and gelatin was added to the silver bromide crystal (hereinafter, internal latent image type core / Referred to as shell particles). Next, 0.4 mg of sodium thiosulfate and 20 mg of poly (N-vinylpyrrolidone) per mol of silver were added to this internal latent image type core / shell emulsion, and the chemistry of the grain surface was measured by heating at 60 ° C. for 60 minutes. Sensitization was carried out to prepare an internal latent image type direct positive emulsion.

Preparation of Emulsion B-1: In the same manner as Emulsion A-1, except that an equivalent amount of gelatino-peptizer was added to 3-thiapentyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid sodium salt (1/6 mol). Ratio) to prepare another internal latent image type direct positive emulsion.

Emulsion E (octahedral internal latent image type direct positive emulsion)
Preparation of: 8% by weight of the invention 3-thiapentyl acrylate / 2-acrylamido-2-methylpropane sulfone containing 13 g potassium bromide and 1.3 g 1,8-dihydrooxy-3,6-dithiaoctane. The temperature is adjusted to 75 in 1000 cc of an aqueous solution of acid soda (1/6 molar ratio).
While maintaining at ℃, pour 0.4M silver nitrate aqueous solution and 0.4M potassium bromide aqueous solution by control double jet method.
300 cc of an aqueous silver nitrate solution was added over 5 minutes while adjusting the addition rate of the aqueous potassium bromide solution so that Br was 1.30. 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 0.4 μm were produced. Next, 1.4 mg of sodium thiosulfate and 0.8 mg of potassium chloroaurate (both were added as an aqueous solution) were added to the silver bromide grains, and a chemical sensitization treatment was performed by heating at 75 ° C. for 80 minutes. It was The chemical sensitized core particles were treated with 0.8 M silver nitrate aqueous solution and 0.8 M potassium bromide aqueous solution by the control double jet method while maintaining the temperature at 75 ° C. as in the core particle preparation. Is 1.30
740 cc of silver nitrate aqueous solution was added over 30 minutes while adjusting the addition rate of the potassium bromide aqueous solution so that This emulsion was washed with water by a conventional flocculation method, and then 3-thiapentyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid sodium (1/6
The average particle size (sphere equivalent diameter) is about 0.7μ
An octahedral silver bromide crystal having a uniform grain size of m (hereinafter referred to as internal latent image type core / shell grain) was obtained. Next, 0.8 mg of sodium thiosulfate and 40 mg of poly (N-vinylpyrrolidone) were added to 1 mol of silver in this internal latent image type core / shell emulsion, and the particles were chemically heated at 60 ° C. for 60 minutes to chemistry of the grain surface. Sensitization was carried out to prepare an octahedral internal latent image type direct positive emulsion. Preparation of Emulsions A-2 to A-5 (Comparative Examples) and B-2 to B-5 (Invention): In each emulsion at the time of shell formation, the metal complexes shown in Table A below were added per mol of silver nitrate.
Emulsions A-1, B-, except that the amounts shown in A were added.
Emulsions A-2 to A-5 and B-2 to B-5 exactly as in No. 1
Was prepared.

[0108]

[Table 1]

Next, a comparative photosensitive element (Sample 101) having the constitution shown in Table B below was prepared using Emulsion A-1.

[0110]

[Table 2]

[0111]

[Table 3]

[0112]

[Table 4]

[0113]

[Chemical 13]

[0114]

[Chemical 14]

[0115]

[Chemical 15]

[0116]

[Chemical 16]

The cover sheet was prepared as follows. The following layers were coated on a polyethylene terephthalate transparent support containing a gelatin-primed anti-light piping dye. (1) 10.4 g / m ^{2 of} an acrylic acid-butyl acrylate (molar ratio 8: 2) copolymer having an average molecular weight of 50,000 and 0.1 g of 1,4-bis (2,3-epoxypropoxy) -butane / M ² containing neutralization layer. (2) Acetyl cellulose having an acetylation degree of 51% 4.3 g /
m ^2, poly (methyl vinyl ether - co monomethyl maleate aid) neutralization timing layer containing 0.2 g / m ^2. (3) Styrene / butyl acrylate / acrylic acid /
N-methylol acrylamide in a weight ratio of 49.7 / 4
A polymer latex emulsion-polymerized at a ratio of 2.3 / 4/4 and a polymer latex emulsion-polymerized at a weight ratio of 93/3/4 of methyl methacrylate / acrylic acid / N-methylol acrylamide have a solid fraction of 6 A layer containing 2.5 g / m ^{2 of the} total solid content, blended so as to be 4 pairs. (4) A layer containing 1 g / m ² of gelatin.

The formulation of the alkaline treatment composition is shown below.
A destructible container was filled with 0.8 g of the treatment liquid having the following composition. 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10.0 g methylhydroquinone 0.18 g 5-methylbenzotriazole 3.0 g sodium sulfite (anhydrous) 0.2 g benzyl alcohol 1.5 cc carboxymethylcellulose Na Salt 58 g Carbon black 150 g Potassium hydroxide (28% aqueous solution) 200 cc Water 680 cc 0.8 g of the treatment liquid having the above composition was filled in a "pressure rupturable container".

Next, the emulsions A-1 of the seventh layer, the thirteenth layer and the nineteenth layer of Sample 101 are shown in Table-A as emulsions A-2 to A-.
5, Sample No. 10 shown in Table-C, changed to B-1 to B-5
2-110 were created.

[0120]

[Table 5]

After exposing the light-sensitive elements 101 to 110 from the emulsion layer side through a continuous wedge of gray, the cover sheets are superposed and the processing solution is placed between both materials.
It was developed using a pressure roller so as to have a thickness of 5 μm. The treatment was carried out at 25 ° C., and after 10 minutes, the transfer density was measured with a color densitometer. The results are shown in Table-D. However, the midpoint sensitivity shown here is the reciprocal value of the exposure amount that gives the midpoint sensitivity of the maximum density and the minimum density, and is expressed as a relative value with respect to the reference sample. The high density sensitivity is the reciprocal value of the exposure amount that gives a density corresponding to the maximum density of -0.2, which is expressed as a relative value with respect to a reference sample.

[0122]

[Table 6]

It is known to use a transition metal compound in an internal latent image type direct positive emulsion, but in all of these prior arts, gelatin is used as a deflocculant during the formation of halogenated grains, and the results shown in Table-D are shown. Therefore, it is apparent that the samples 101 to 103 are inferior to the samples 104 and 105.
The use of the peptizer of the present invention in place of gelatin is known, for example, in U.S. Pat. No. 3,615,624, and all of these prior arts relate to pre-fogged direct positive emulsions. It is clear from the results of Table D that Sample 101 is inferior to Sample 106 only by replacing gelatin in the internal latent image type direct positive emulsion as in the present invention with the peptizer of the present invention. On the other hand, in the internal latent image type direct positive emulsion, gelatin was replaced with the deflocculant of the present invention, and the transition metal compound of the present invention was used.
07-110 is excellent. In particular, Samples 109 to 110 are significantly superior to Samples 107 and 108 by using the hexacoordinated cyano complex.

Example-2 First, a method for preparing a silver halide emulsion will be described. Preparation of emulsion C-1 (octahedral internal latent image type direct positive emulsion):
In 1000 cc of 8% by weight gelatin aqueous solution containing 13 g of potassium bromide and 0.05 g of 1,8-dihydrooxy-3,6-dithiaoctane, 0.4 M silver nitrate aqueous solution and 0% while maintaining the temperature at 75 ° C. While the addition rate of the 4M potassium bromide aqueous solution was adjusted by the control double jet method so that the pBr was 1.30, 300 cc of a silver nitrate aqueous solution was added over 40 minutes. When the addition is complete, the average particle size (sphere equivalent diameter)
An octahedral silver bromide crystal having a uniform grain size of about 0.8 μm (hereinafter referred to as core grain) was produced. Next, 0.7 mg of sodium thiosulfate and 0.4 mg of potassium chloroaurate were added to the silver bromide grains (both were added as an aqueous solution), and the mixture was heated at 75 ° C. for 80 minutes to perform a chemical sensitization treatment. It was In the same manner as in the core particle preparation, the core particles chemically sensitized in this manner were treated with 0.8M silver nitrate aqueous solution and 0.8M potassium bromide aqueous solution by a control double jet method while maintaining the temperature at 75 ° C. pBr 1.3
An aqueous solution of silver nitrate (740 cc) was added over 60 minutes while controlling the addition rate of the aqueous solution of potassium bromide so as to be zero. This emulsion was washed with water by a conventional flocculation method, and gelatin was added thereto to form an octahedral silver bromide crystal having an average particle size (sphere equivalent diameter) of about 1.4 μm (hereinafter referred to as internal latent image type). Referred to as core / shell particles). next,
In this internal latent image type core / shell emulsion, the amount of silver per mol of silver was 0.
4 mg of sodium thiosulfate and 20 mg of poly (N-vinylpyrrolidone) were added, and the grain surface was chemically sensitized by heating at 60 ° C. for 60 minutes to prepare an octahedral internal latent image type direct positive emulsion.

Preparation of Emulsion D-1: In the same manner as Emulsion C-1, except that a gelatin peptizer was used in an equal amount of 3-thiapentyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid sodium salt (1/6 mol). Another octahedral internal latent image type direct positive emulsion was prepared. Preparation of Emulsions C-2 (Comparative Examples) and D-2 (Invention): Except that the metals shown in the following Table-E were added to the respective emulsions in the amount shown in Table-E per mol of silver nitrate in each emulsion during shell formation. And Emulsion C- exactly as Emulsions C-1 and D-1
2 and D-2 were prepared.

[0126]

[Table 7]

Next, a comparative photosensitive element (Sample 201) having the constitution shown in Table F below was prepared using Emulsion C-1.

[0128]

[Table 8]

[0129]

[Table 9]

[0130]

[Table 10]

Next, the emulsions C-1 of the seventh, thirteenth and nineteenth layers of Sample 201 are emulsions C-2 and D- shown in Table E.
1 to D-2, and samples 202 to 20 shown in Table-G
Created 4.

[0132]

[Table 11]

The photosensitive elements 201-204 were exposed from the emulsion layer side through a continuous gray wedge and then overlaid with the cover sheet of Example 1 and between Example 1 between the two materials.
The treatment liquid of (1) was spread using a pressure roller so as to have a thickness of 75 μm. The treatment was carried out at 25 ° C., and after 10 minutes, the transfer density was measured with a color densitometer. The results are shown in Table-H.
Shown in. However, the midpoint sensitivity shown here is the reciprocal value of the exposure amount that gives the midpoint sensitivity of the maximum density and the minimum density, and is expressed as a relative value with respect to the reference sample. The high density sensitivity is the reciprocal value of the exposure amount that gives a density corresponding to the maximum density of -0.2, which is expressed as a relative value with respect to a reference sample.

[0134]

[Table 12]

It is known to use a transition metal compound in an internal latent image type direct positive emulsion, but in all of these prior arts, gelatin is used as a deflocculant during the formation of halogenated grains, and the results shown in Table-H are shown. Therefore, it is clear that the sample 201 is inferior to the sample 202. The use of the peptizer of the present invention in place of gelatin is known, for example, in U.S. Pat. No. 3,615,624, and all of these prior arts relate to pre-fogged direct positive emulsions. In the internal latent image type direct positive emulsion as in the present invention, simply replacing gelatin with the deflocculant of the present invention shows that the results of Table-H indicate that Sample 201 is more difficult than Sample 203.
Is clearly inferior. On the other hand, in the internal latent image type direct positive emulsion, by replacing gelatin with the peptizer of the present invention and using the transition metal compound of the present invention,
Sample 204 is superior to samples 201 and 203.

[0136]

The present invention provides an internal latent image type direct positive silver halide emulsion having a high sensitivity and a large difference between the maximum density and the minimum density, and a color diffusion transfer photographic light-sensitive material using the same.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 8, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

On the other hand, European Patent No. 0,336,425,
U.S. Pat. And a silver halide emulsion having excellent gradation gradation stability and improved low illumination failure. Here, it is recognized that the hexacoordinated transition metal complex is accommodated in the void space of a single halide ion inside the crystal structure,
This is different from the conventional belief that transition metals are incorporated into silver halide grains as single ions or atoms. However, in this patent the types of transition metals are limited to rhenium, ruthenium, osmium and iridium, but not to cobalt , iron, manganese or chromium . Further, it does not describe an internal latent image type direct positive silver halide agent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 8/10 504 8910-2H

Claims (4)

[Claims] 1. A thioether structure in at least one side chain
A silver halide emulsion grain is formed by using a polymer having a repeating unit derived from an ethylenically unsaturated monomer having a seed as a peptizer, and manganese, chromium, copper is used for the formation of the silver halide emulsion grain. Zinc, cadmium, lead,
An internal latent image type direct positive silver halide emulsion containing at least one metal selected from bismuth, rhenium, and Group 8 metal of the periodic table. 2. The metal added is represented by the following general formula (I):
The internal latent image type direct positive silver halide emulsion according to claim 1, which is a hexacoordinated cyano complex represented by: General formula (I) [M (CN) ₆ ] ^n-In formula (I), M is Ir, Co, Ru, Os, Re, F.
represents e, Mn or Cr, and n represents 3 or 4. 3. The internal latent image type direct positive silver halide emulsion according to claim 1, wherein the added metal is lead. 4. A silver developer having on a support at least one light-sensitive silver halide emulsion layer in combination with a dye image-forming substance, said dye image-forming substance being represented by the following general formula (II): A non-diffusible compound releasing a diffusible dye or a precursor thereof in relation to, or a color diffusion transfer photosensitive material comprising a compound whose diffusivity of itself is changed,
2. At least one of the silver halide emulsion layers is claim 1.
4. A color diffusion transfer light-sensitive material comprising the internal latent image type direct positive silver halide emulsion according to claim 3. Formula (II) (DYE-Y) _n -Z {DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, 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. }