JPS63205653A - Color recording material and color image forming method - Google Patents

Abstract

PURPOSE:To improve image quality such as hue, image sharpness and edge sharpness and to provide a variety of tones by incorprating a high contrasting agent or high contrasting agent precursor which can form a color image having >=3 max. gamma value by color development into the titled material. CONSTITUTION:The color recording material constituted by forming a photosensitive layer contg. a photosensitive silver halide emulsion and color couplers on a base contains the high contrasting agent or high contrasting agent precursor which can form the color image having >=3 max. gamma value by the color development. The term 'gamma' refers to the gradient of a characteristic curve expressed by the logarithm of the color filter density of the respective colored images obtd. by the color development of the color recording material and exposure. A hard copy which has the excellent image quality such as hue, image sharpness and edge sharpness and has a variety of tones is thereby obtd. from the original constituted of the images consisting of line images and dots.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is applicable to printing from an original consisting of an image composed of line drawings or knitting points, or to color recording by digital output from digitized information. This invention relates to the /Sloge/silver oxide color recording material used, and in particular to a full-color recording material with excellent reproducibility of hue, image sharpness, and gradation.

(Prior Art) Conventionally, electrophotography and black-and-white silver halide photosensitive materials have often been used to print or copy original text and line drawings and printed matter.

Recently, in addition to conventional hard copy originals such as photographs and printed matter, soft originals have also appeared with the advancement of electronic recording image systems, and there has been a strong demand for a method to make hard copies of these, and in particular there is a demand for colorization. has become stronger. In response to this, heat-sensitive methods such as methods using sublimation dyes and methods using heat transfer methods, improved electrophotographic methods, inkjet methods, and pressure-sensitive recording methods,
Furthermore, these combined systems are being used. These methods have their own advantages, such as being simple, quick, dry, low cost, and lightweight and compact, but at present they are inferior in terms of image quality such as the most important color image hue, image sharpness, and gradation reproduction. be. Therefore, an improved method has been used to take advantage of the photosensitivity and image quality of halog/silver oxide, and to improve the conventional color printing method for the purpose of copying from the original. For example, Ciba Geigy Japan's CB copy system, Konishirokusha's Color 7 copy system, 3M
Color Dry Silver System, etc. Although the image quality of these materials has been improved in terms of hue and image sharpness, they are inferior in recording from the original digital reproduction method, and there is room for improvement in edge sharpness and gradation reproduction. A printing system that uses the . However, it is desirable to improve these defects by improving the recording material, even though there is no change in appearance.

On the other hand, in the black-and-white development method, it is said that when a photosensitive silver halide photosensitive material is developed using a hydroquinone-only developing solution, ultra-high contrast black-and-white images are formed due to so-called contagious development (for example, T, H, James @
The Ory of the l'hoto
graphic process 4th edition g1.4 chapter 5
Section 419-420 (1977, MacMilla
n Pub, co, , INC, Publishing) etc.). When a light-sensitive silver halide photosensitive material is used in combination with Maku hydrazi/compound and a development accelerator such as Ami-7, it is possible to quickly and stably form an ultra-high contrast bright white image similar to infectious development. known (for example, Japanese Patent Application Laid-Open No. 53-16
No. 623, No. 53-20922, No. 53-667
No. 32, No. 53-77616, No. 8471-8471
No. 4, No. 53-137133, No. 54-3773
No. 2, No. 54-40629, JP 60-1120
No. 34, No. 60-140340, No. 56-678
No. 43, Special Application No. 1983-64199, Magu Special Application No. 1983-
232086 etc.).

However, these documents do not mention anything about the application of these techniques to color photosensitive materials.
In addition, it is generally considered that it is extremely difficult to develop a color development process for forming various colored images using a black-and-white development method as a color developing agent.

On the other hand, there is a method of using a development accelerator-releasing coupler (so-called DAR coupler), which contains a hydrazide/derivative group in a color light-sensitive material and has a residue i that separates during color development, for the purpose of accelerating development, increasing sensitivity, and improving graininess. Are known. Due to its development accelerating effect, color 1-images can be toned to # when r is 3 or less, but graininess worsens under this condition, so in conventional color technology, separate steps are taken to improve graininess t. Use of other techniques or conditions was mandatory. It is also said that if graininess is not deteriorated, high contrast will not occur as much (for example, Japanese Patent Application Laid-Open No. 57-1
No. 50845 and Patent Application No. 60-147779 (R).

In conventional color technology, the main focus has been on suppressing the increase in contrast of color images, but suppressing the increase in contrast accompanying improvement in graininess is advantageous for the purpose of the prior art.

Therefore, the current situation is that a technology for increasing contrast in the color field has not yet been discovered.

The purpose of the present invention is to make it possible to make a copy with excellent image quality such as hue, image sharpness, edge sharpness, etc., and rich gradation from an original composed of an image composed of line drawings, halftone dots, etc. To provide color recording materials. The next objective is to
The present invention provides a color recording material that can make the above-mentioned superior node copies by digital output from software information. Our ninth goal is to provide full-color recording materials that anyone can process stably and over a long period of time. Other objectives will be apparent from the description herein.

(Ninth Means for Solving the Problems) The above object of the present invention is to provide a color recording material comprising a photosensitive layer containing a photosensitive silver norogenide emulsion and a color coating on a support. It has been found that it can be coupled to a color recording material characterized by containing a contrast-enhancing agent or a contrast-enhancing agent precursor capable of forming a color image having a maximum γ value of 3 or more by development.

The present invention differs from any conventional color technology in that it forms super-high contrast micro-images like so-called contagious development and reduces graininess in the process of color development, particularly color development, particularly color development using paraphenylene/diamide/derivatives. Rather, it is intended to make the grain coarser and make the smallest particle unit smaller, thereby significantly increasing the edge contrast of the micro image. For this purpose, it is preferable to match the characteristics of the organic material used and the photosensitive silver halide grains, and for nails, it is preferable to match the composition and development conditions of the color developer to this purpose.

In the present invention, "γ" refers to the slope of the characteristic curve expressed by the logarithm of the color filter density and the exposure amount of each color image seen after color development on a color recording material. The color filter used in the present invention is preferably a color filter that mainly transmits light with the main absorption wavelength of various colored images, for example, a red (R) filter, a green (G) filter, or a blue (B) filter.
) As filters, Eastman Kodak Co.'s Latte/Filter Shoulder 92.493 and Makuwa Fu 94 are used, respectively. In the present invention, the contrast enhancer (in a broad sense) refers to a material or frame that has the effect of further increasing Kr*', or a photosensitive layer whose r value is 3 or more, preferably 5 or more,
More preferably, the density is 10 or more, and even more preferably, the density is from base density 10 capri to base density 10 fog +1
．． If it is 10 or more in the density range of 0, it is called the material used for the color.

Therefore, even if the material is the same, the purpose of the photosensitive material used.

Photosensitive silver halide emulsion or color toy 1#l! Liquid machining agents cannot necessarily be defined as normal-pressure contrast agents depending on the color development process. Further, the contrast enhancer (in a broad sense) can also serve other purposes or functions.

The contrast enhancing agent (in a broad sense) used in the present invention can be preferably selected from the group of compounds represented by the following general formula [I] and general formula [■].

General formula [I] ,,-2-.

(In the formula, 2 represents a nonmetallic atom necessary to form a 5- to 6-membered heterocycle, 2 may be substituted with a substituent, R is an aliphatic group, and R2 is hydrogen an atom, an aliphatic group or an aromatic group.

H and R may be substituted with a substituent. However, R1
, R2, and zl, at least one of them is an alkynyl group, an acyl group, a hydrazine group. Forms a pyridinium skeleton.KM%R
and at least one of the substituents of 2 is X −tL −
)-7k. In this case, /, nl is 0 or 1, and ml is 0 or 1) or the general formula (
11) (In the formula, 1 and 21 represent an aliphatic group, an aromatic!A, or a heterocyclic group r; R22 is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or an Representation: G may have a carbonyl group, sulfonyl group, sulfoxy group, phosphoryl group, or iminomethylene group (MN=C\).X, L,
m2 is the same as Xl, Ll, and ml of general formula [I], respectively. , 23 and it24 each represent a hydrogen atom, or one of them represents a hydrogen atom and the other represents any one of a kaalkylsulfonyl group, an arylsulfonyl group, or an acyl group. A hydrazone structure (〉N-5-c''>'t) may be formed by including G, 1(, R and hydrazi/nitrogen.The above-mentioned groups may be substituted as substituents if possible. (May be substituted.) Among these compounds, those having a hirazine derivative group are particularly preferable.Furthermore, it is preferable to use a compound having a hirazine derivative group. , appropriate hydrophobicity 1
The next step is to introduce a ballast group into a compound that can be properly fixed in the vicinity of the development nucleus. This is particularly important in the case of color photosensitive materials having a multilayer structure. Furthermore, a coupler having an active methylene residue or a residue that releases a contrast enhancer during color development, ie, a contrast enhancer precursor, is preferred.

To explain in more detail in general formula (1), the heterocycle completed by Z is, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium. , imidazolium,
Mention may be made of tetrazolium, i/tho9rhenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxacillium, naphthooxacillium, naphtopyridinium and be/zooxazolium nuclei.

Examples of the substituent for 2 include an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, and an alkylthio group.

Arylthio group, acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, suifamoyl group, sulfo group, cyano group, ureido group, +7 ethane group, carbonate ester group.

Examples include hydrazi7 group, human 2sine group, and imino group. As the substituent for 2, at least one is selected from the above substituents, but if two or more are selected, they may be the same or different.

(9) The above substituents may be further substituted with these substituents.

Furthermore, as a substituent for 2, Z
It may have a heterocyclic quaternary anthonium group completed by: In this case, it takes a so-called dimer structure.

The heterocycle completed by zl is preferably quinolinium, k/zothiazolium, be/zimidazolium,
Pyridinium, acridinium, phenansclidinium, naphtopyridinium and isoquinolinium nuclei are mentioned. More preferred are quinolinium, benzothiazolium, and naphtopyridinium, and most preferred is quinolinium.

The aliphatic group of R and R is an unsubstituted alkyl group having 1 to 18 carbon atoms and a substituted alkyl group having 1 to 18 carbon atoms in the alkyl moiety. The following are mentioned. The aromatic group represented by OK has 6 to 20 carbon atoms, such as a phenyl group, a 7-tyl group, etc. ◎As a substituent, Things can be given. R is preferably an aliphatic group, most preferably a methyl group and a substituted methyl group.

At least one of the groups represented by Ri, R2 and 2 has an alkyl group, an acyl group, a 1-12dine group or a hydrazo group, or R1 and R2 It forms a 6-membered ring and forms a dihydropyridinium core, which may be substituted with the 9 groups mentioned above as substituents for the group represented by 2. Among the hydrazi7 groups, acyl groups and sulfonyl groups can be used as substituents.
-V is preferred. The hydrazo y group preferably has an aliphatic group or an aromatic group as a substituent.

As the acyl group, al, for example, formyl group, aliphatic group or aromatic ketone is preferable.

When at least one of the substituents on the group or ring represented by K1, R2 and 2 is an alkynyl group or an acyl group, or when R and R are linked to form a dihydropyridinium core. is preferable, and it is most preferable that it contains at least one alkynyl group. Preferred examples of the adsorption group to silver halide which is removed by O Examples include telocyclic groups.

These are described as substituents for 2 and may be substituted with the following. The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thiourido group, etc.).

The mercapto group of
, 3,4-thiadiazole, etc.) are preferred.

The 5- to 6-membered nitrogen-containing heterocycle represented by X is one consisting of a combination of nitrogen, oxygen, sulfur, and carbon,
Preferably, it produces iminosilver, such as benzotriazole or ceralyl.

X is a group t- that can be released by reacting with the oxidized product of the color developing agent
As expressed, for example, X is an active methylene residue (Cp) of a coupler, which may be a colored coupler residue or a colorless coupler residue.

Here, typical examples of yellow couplers among couplers are U.S. Pat.
No. 10, No. 3,265,506, No. 2.298,44
No. 3, No. 3,048,194, No. 3.447,928
It is stated in the number etc. Among these yellow couplers, acylacetamide 1 derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred.

SifF- As the yellow coupler residue, those represented by the following general formulas (X-1) and (X-1i) are preferred, where * represents the position to which another residue is bonded.

Here, R101 represents a diffusion resistance having a total carbon number of 8 to 32, and R102 represents a hydrogen atom, a total of 1 to 9...Rogge/atoms, a lower alkyl group, or a lower alkoxy group, or a total carbon number of 8 to 32. 32 diffusion-resistant groups. When R102 is 2 to 9, they may be the same or different.

A typical example of Mai/Ta coupler is U.S. Patent No. 2.600.
, No. 788, No. 2,369,489, No. 2.343,
No. 703, No. 2,311,082, No. 3.152,8
No. 96, No. 3,519,429, No. 3.062,65
No. 3, No. 2,908,573, etc. Among these my/ta couplers, pyrazolo/or bisizoloazoles (pyrazolopyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, etc.) are preferred.

Therefore, as the mi/ta coupler residue, those represented by the following general formulas (X-1n), (X-fV) and (, X-V) are suitable. Here, R101 has 4 carbon atoms. represents a diffusion-resistant group of 8 to 32, R102 represents a nitrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, and 1t represents a substituted phenyl group. zlol represents a group of nonmetallic atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms; good.

A typical example of a cyan coupler is U.S. Patent No. 2.772,
No. 162, No. 2,895,826, No. 3.002,8
No. 36, No. 3,034,892, No. 2.474,29
No. 3, No. 2,423,730, No. 2.367,531
No. 3,041,236, etc. Among these cyan couplers, phenols or 7-tols are preferred.

Therefore, as the shear/coupler residue, those represented by the following general formulas (X-Vt) and [X-■] are suitable.

In the formula, R101 represents an alkyl group, an aryl group, a heterocyclic group, or an amino group, and these groups may be further substituted. Typical examples of the substituted amino group include an arylamino group and a nitrogen-containing heterocyclic group 1i-.

R102 is a halogen/atom, an alkyl group, an alkoxy group,
Acylamino, IIi, or alkoxycarbo. Nyl group 't-'-1 These groups may be further substituted. When 2 to 3 R102s are present, they may be the same or different, or two R102s may be linked to each other to form a 5- to 6-membered saturated or unsaturated carbocycle or heterocycle. good. These rings may be further substituted. Examples of the heteroatoms forming the heterocycle include nitrogen, oxygen, sulfur, etc.@A specific example of a ring in which the above-mentioned heterocycles are condensed is 3,4-dihydrocarbostyryl, etc.◎R103 represents an alkyl group or an aryl group, and these groups may be further substituted.

R104 has the same meaning as R102, and when two R104s are linked together to form a 5- to 6-membered saturated (7 or unsaturated carbon ring or heterocycle), a group that can be further substituted on these rings. As such, the groups listed above for R102 are applicable, and sulfonamide groups and the like are also applicable.

In order to impart diffusion resistance to the contrast enhancer precursor having a Katzler residue represented by the general formula (X-Vl) or [X-■], the total carbon number of R101 and R102 or R103 and R104 is 8 to 80. A fist that is .

Xl reacts with the oxidized form of the color developing agent and leaves a group t
- As a place to express, for example,
It may also be a residue that releases a hardening agent. These are hydroquinone and catechol.

You can choose from among those with a skeleton structure such as O-aminophenol and P-7 minophenol.

An example of a protective group that is removed during color development is an acyl group.
For example, when the @L1)- residue is directly connected to the benzene ring of the contrast-enhancing agent-releasing residue, it may be the so-called precursor of -　-, which constitutes the He ring. The 〇-aminophenol t7t is bonded to the high-contrast release residue via this group, and the high-contrast release residue has a p-aminophenol skeleton (including the case of a fused ring).9゜-LL)-g residues are attached directly to their benzene rings (ie, forming a sulfo/amide group).

Furthermore, X may be a ballast residue ◎The ballast group is a group that provides appropriate diffusion resistance, has a size and shape that provides non-diffusivity to the coupler, and connects multiple leaving groups to E-9. It may be in the form of a polymer, and may have an alkyl group and/or an aryl group that provides bulk non-diffusibility. In the latter case, the alkyl group and /l
The total number of carbon atoms in the aryl group or aryl group is preferably about 8 to 32. (varas) fi has a group for bonding to the Kubrifug position of the coupler, and an alternative thereof is -〇-1-S-1-N=N-1o O-N<.

The -tL ke group is a divalent linking group, and the divalent linking group represented by L is an atom or atomic group containing at least one of C%LS%U.

Specifically, examples include alkylene/group, alkenylene group, alkynylene/group, aryle/group, -0-1-S-1,NH
-1-N-1-CO-1-8O-1-8O2-1-N-
Nine groups selected from N-, carbo/amide group, thioamide group, sulfonamide group, ureido group, thioureido group, and heterocyclic group (these groups may have a substituent t), etc. consists of a combination of these. Further, when X is a group capable of reacting with and leaving the oxidized form of a color developing agent, it may be a so-called timing linking group. As this group, reducing compounds (hydrazi/
, hydrazide, hydrazo/, hydroquino/, catechol, p-aminophenol, p-phenylenediamine,
1-phenyl-3-pyrazolone, enami/, aldehyde, boriaone, acetylene/, aminoborane, tetrazolium salt, quaternary salt substituted for ethylene bispyridinium salt, carno (di/sh4 $), or silver sulfide during development. The compound WJ (thiourea, thioamer, dithiocarno oligomate) that can form

Examples include those consisting of rhodanine, thiohida/toi/, and thiazolidi/thi. It also bonds more with sulfur atoms. When removing a Taimi/g group, a single molecule substitution reaction is used as described in US LIII% Patent No. 4,248,962, Japanese Patent Application Laid-Open No. 57-56837, etc., and British Patent No. 2,072, No. 363 A, JP-A-57-15423
No. 4, JP-A-57-188035, JP-A-54-98
728 etc., 7tT via a conjugated group in the molecule.
There are many things that use IL child movement.

As the adsorption group for the halogenated group in
Fatty derivatives from compounds having a heterocyclic ring with a mercapto group 1
The following groups are mentioned.

In general formula (Ii), R21 may be substituted with a substituent, and examples of the substituent include the following. These groups may be further substituted. For example, alkyl groups, aralkyl groups, alkoxy groups, alkyl or aryl groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups, aryl groups, alkyl groups, Examples include arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halo group, cyano group, sulfo group, and carboxyl group.

Among these, ureido groups are particularly preferred.

These groups may be linked to each other to form a ring when possible.

R21 is preferably an aromatic group, an aromatic heterocycle, or an aryl-substituted methyl group, and < and < are preferably aryl groups (eg, phenyl group, naphthyl group, etc.).

Among the groups represented by R22, preferred are a hydrogen atom and alkyl-11! (?11 example methyl group)'! 9 is an aralkyl group (eg, O-hydroxybenzyl, etc.), and a hydrogen atom is particularly preferred.

As the substituent for R22, in addition to the substituents listed for R21, for example, an acyl group, an acyloxy group,
Alkyl or aryloxycarbonyl groups, alkenyl groups, alkynyl groups and nitro groups are also applicable.

These substituents may be further substituted with these substituents. If possible, these groups may be randomly linked to form a complete ring.

x21 or kL22. Among these, R21 may contain a diffusion-resistant group such as a coupler, a so-called ballast group, and is particularly preferable when linked with a ureido group).

Group X that promotes adsorption to NW of silver halide grains →
) There may be 7 pieces. Here, X is X in general formula [I]
and is preferably a thioamide group (excluding thiosemicarbazide and its substituted products), a mercapto group, or a 5- or 6-membered nitrogen-containing heterocyclic group. L
represents a divalent linking group and has the same meaning as L in general formula [I].

m2 is 0 and m2 is 1.

More preferably, X is an acyclic thioamide group (e.g., a thioureido group, a thiourethane group, etc.), a cyclic thioamide group (i.e., a mercapto-substituted nitrogen-containing heterocycle, such as a 2-mercaptothiadiazole group, a 3-mercapto-
1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobe/zoxazole group, etc.), or nitrogen-containing heteajJl group (e.g. /citriazole group, be/zimidazole group, indazole group, etc.).

The most preferable X differs depending on the photosensitive material used. For example, when using a coloring material (so-called coupler) that forms a dye through a Kablihug reaction with an oxidized product of a p-phenylenediamine developer in a color photosensitive material, X2 is a mercapto-substituted nitrogen-containing heterocycle, or an iminosilver A nitrogen-containing heterocycle forming is preferred. In addition, in color photosensitive materials, a coloring material (so-called D
RR compound), X is preferably an acyclic thioamide group or a mercapto-substituted nitrogen-containing heterocycle. Hydrogen atoms are preferred as R23 and R24.

Examples of these compounds and their synthesis methods can be found in, for example, the Research Die-c
losiure) magazine 422,534 (issued January 1983, 50-54), and 23,213 (198
(Published in August 2003, pp. 267-270)
52-47,326, JP-A-52-69,613, JP-A-52-3,426, JP-A-55-138,742,
No. 60-11,837.

U.S. Patent No. 4.306,016 and U.S. Patent No. 4,471,
No. 044, etc., as well as U.S. Patent Nos. 4,030,925, 4,080,207, and 4,031,127
No. 3,718,470, No. 4,269,92
No. 9, No. 4,276,364, Same! 4,278,7
No. 48, No. 4,385,108, M4,459,
No. 347, No. 4,478,928, No. 4,560
, No. 638, British Patent No. 1g2,011,391 B,
JP-A-54-74.729, JP-A No. 55-163,533
No. 55-74,536, and No. 60-179,7
No. 34, etc., as well as %Kokai No. 57-86,829, U.S. Pat. No. 2,563,785 and No. 2,588,98
It is stated in No. 2.

Counter ions Y' for charge para/s include bromine ion, chloride ion, iodine ion, p-, lue/sulfo/acid ion, ethyl sulfonate ion, perchlorate ion, trifluoro meta/sulfonoic acid io/, thiogua/
The high contrast agent used in the present invention or the precursor of the high contrast agent used in the present invention may be added to the high contrast agent/silver oxide emulsion, depending on the structure of the compound used, preferably 1×10 mol to I×10 mol, more preferably 1×1
0-2 moles to 10 moles are used. This contrast enhancer may be added to other hydrophilic colloids 1-. It can also be added to the prebath or color developing solution described in JP-A-58-178350 to take advantage of the effect of increasing contrast, but in this case, it is preferable to use 10 mol to 10 mol of the total amount of the developer. More preferably, the amount is 10 mol to 10 mol. Specific examples of the contrast enhancing agent represented by the general formula [I] or (11) according to the present invention are shown below, but the present invention is not limited thereto.

1-(1) 2-methyl-1-propargylquinolinium phromide-12) 2-methyl-1-propargylquinolinium phromide-(3) 2-methyl-1-(3 -(2-(4-methylphenyl)hydrisono]butyl)quinoliniumiosito-(413,4-dimethyl-dihydropyrido(2,1-
1)) Be/dithiazolium bromide-(5) 6-nitoxythiocarponylamino-2-
Norinium trifluoromethate in methyl-1-propargyl (6) 2-Methyl-6-(3-phenylthio9reido)-1-propargylquinolinium bromide-(7
) 6-(5-be/citriazole carboxamide)
-2-Methyl-Wyzrugylquinolinium trifluorometa/sulfonate trifluoromethanesulfonate-(9) 6-(3-(5-mercapto-thiadiazol-2-ylthio)furobyl]urei)')-2-methyl -1-propargylquinolinium trifluorometa/sulfonate 1016-L5-mercaptotetrazol-1-yl)
-2-Methyl-1-propargylquinolinium bromide 1l-(1) 1-formyl-2-(4-(3-(2
-methoxyphenyl)ureidocuphenyl)hydrazi-+2) 1-formyl-2-(4-[3-(3-1
:3-(2,4-di-tert-hard/tylphenoxy)
propyl]ureido)phenylsulfonylaminoco-phenyl)hydrazi/ -(3) 1-formyl-2-(4-(3-(5-mercaptotetrazol-1-yl)pe/zamido]phenyl)hydrazi/ -(431 -formyl-2-(4-(3-(3-(5-
Mercaptotetrasol-1-yl)phenylthureido)phenyl]hydrazine-(5J 1-formyl-2-(4-(3-(N-(
5-mercapto-4-methyl-1,2,4-triazol-3-yl)carbamoyl]prono/amido)phenyl]hydrazine-(611-formyl-2-(4-(3-(N-(4-
(3-mercapto-1,2,4-triazol-4-yl)phenyl]carbamoyl)-pro/ce/amido]phenyl)hydrazine-(7) 1-formyl-2-(4-(3-(N- (5
-Mercapto-1,3,4-thiadiazol-2-yl)carbamoyl]propa/ami)")phenyl]hydrazi/ -1812-(4-((/citriazole-5-carboxydo)phenyl2-1-formylhydrazine- (912-(4-(3-(M-(be/citriazole-5-carboxamide)carbamoyl)pronoyymyy
)yenyl]-1-formylhydrazine-QG 1-$lumylJ-(4-(1-(N-7zylcarbamoyl)thiosemicarbazide]phenyl)hydrazi/ -aυ 1-formyl-2-(4-[3 -(3-phenylthioureido)be/zamido]phenyl)hydrazi/ -Q3 1-formyl-2-(4-(3-hexylureido)phenyl]hydrazi/ 1-C10) ■-α4 ■-αri I U -21l-(171 -as -as OR ■-■ ■-Q11 O(CH,)□, cIi3 ■-■ 11-+23 U-a! lump t+-S ■-(A) 0 interval n-■ IJ ■-(A) H n-(2) H ni3 -on ■-(To) H Su ■-ron-(2) ■-(To) The high contrast agent or its precursor used in the present invention is The above may be combined.

In order to introduce the compound of the present invention into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 can be used. For example, 7 tar acid ester in alkali ()phthyl a/L/ -I'll dioctyl phthalate), υノI! I2 ester (diphenyl 7
male 7-o-7ate, triphenyl 7-o-7ate, tricresyl phosphate, dioctyl butyl 7-othate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate)
, alkylamide (diethyl laurylamide),
Fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (
For example, trimezine/#R tributyl), or boiling point 3
Dissolved in an organic solvent at 0°C to 150°C, such as lower alkyl acetate such as rn#t ethyl, butyl acetate, propio/ethyl acetate, secondary butyl alcohol, methyl isobutyl keto/, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. It is then dispersed into hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, %min No. 51-39853, Japanese Patent Application Laid-open No. 51-5994.
The dispersion method using polymers described in No. 3 can also be used.

When the contrast enhancing agent has an acid group such as carbo/acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

In the present invention, the distribution of silver halide grains is preferably monodisperse and smooth. When the contrast-enhancing agent of the present invention is present, development nuclei are generated in a specific portion, and as development progresses, development is contagiously induced in nearby or adjacent particles, causing the particles to rapidly turn into dots. If the grain structure, especially the structure of the silver halide grains used, is characterized and the photosensitivity thereof is made uniform, the generation of development nuclei will occur substantially simultaneously, particularly in the early stages of development. Silver halide grains with a single sensitivity dispersion preferably stop development at the initial stage of development, and are observed without any change in the appearance of the nozzle/forming scissors, and development nucleus formation is observed. Here, the development initialization refers to the time from 1 to 10 of the color development time.

In the present invention, by making the distribution of the No-Rogge/silver oxide grains monodisperse, it is possible to improve the gradation of the intermediate tones and the leg portions. Alternatively, a photosensitive material with an r value of 5 or more can be prevented from decreasing due to other factors and can be maintained.

Monodisperse as used herein refers to an emulsion having a grain size distribution in which the coefficient of variation S/r regarding the grain size of silver halide grains is 0.25 or less. Here, 7 is the average particle size and S is the standard deviation regarding the particle size. That is, if the grain size of each emulsion grain is rl and the ridge is nl, then the average grain size is 7.
is expressed as a foot, and its standard deviation S is defined as .

In the present invention, the individual grain size refers to a silver emulsion prepared by T.H.
) et al. ``The Theory of the Photographic Process J''
he Photogr-apic Process
) 3rd edition 36-43 Sada, published by Makumira/sha (196
It is determined by the diameter equivalent to the projected area, which corresponds to the area projected when a microphotograph is taken using a method well known in the commercial world (usually by electron microscopy or photography), as described in 1996). Here, the projected equivalent diameter of silver halide grains is defined by the projected area of silver halide grains and the diameter of a fine circle, as shown in the above-mentioned book. Therefore, even if the shape of the silver halide grains is other than spherical (for example, cubic, octahedral, tetradecahedral, tabular, potato-shaped, etc.), it is possible to determine the average grain size Y and its deviation S as described above. It is.

The variation factor related to the grain size of silver halide grains is 0.25
or less, preferably less than 0.20 tL<
is 0.15 or less.

7 of the silver halide grains is preferably 0.1μ to 2μ
, more preferably from 0.2μ to 1μ.

The shapes of silver halide grains are hexahedral, octahedral, dodecahedral,
It is preferable to have a regular crystal shape (normal crystal grain) such as a tetradecahedron, or it may be an irregular crystal shape such as a spherical shape, a potato shape, or a tabular shape with an aspect ratio of 5 or more.

The halogen composition of the silver halide grains is silver bromide, silver nitrogen,
Silver iodide is added to each of the silver chlorobromide in an average amount of 0 to 10 moles, preferably θ to 3 moles to speed up development. The halogen composition is preferably particles with a uniform structure, core/shell 211 structure, or multiple heterostructure.

It can be determined based on the clear layered structure and the method of 411w1@folding mentioned here. An example of applying the X-ray diffraction method to silver halide grains is B, Hirschi's literature Journal of Photography Inc.
tographic 5science) gig l
It is described in Volume 9 (1962), page 129 onwards. When the lattice constant is determined by the halogen composition, a diffraction peak occurs at a diffraction angle that satisfies the Plack condition (24 sin #mnλ).

Regarding the measurement method of X-ray diffraction, see Basic Chemistry Course 24 r.
It is described in detail in "X-ray analysis" (Kyoritsu Shuppan) and "X-ray diffraction guide" (Rigaku Denki Co., Ltd.). The standard measurement method uses Cu as a target and uses β rays as #1 source for Cu (tube voltage 40KV, tube current 60mA).
This is a method for determining the diffraction plane Iw of the (220) plane of silver halide. In order to increase the resolution of the measuring device, the width of the slit (divergent slit, light receiving slit, etc.), the time constant of the device,
It is necessary to appropriately select the scanning speed and recording speed of the goniometer and confirm the measurement accuracy using a standard sample such as silico.

In order to judge whether a silver halide emulsion has a layered structure or an emulsion in which two types of silver halide grains coexist as described above, in addition to the X-ray diffraction method, the IPMA method (Wlaatron -Probe Micro.

This is possible by using the Analysssr method).

In this method, a well-dispersed slurry is created so that the emulsion grains do not come into contact with each other, and then an electron beam is irradiated. Elemental analysis of extremely small parts can be performed by X-ray analysis using electron beam excitation.

By this method, the halogen composition of each particle can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each particle.

The photosensitive silver halide monodisperse emulsion used in the present invention may contain silver halide/silver grains that are less sensitive than the silver halide grains or are not chemically sensitized.

In particular, when the development progresses quickly, when silver chlorobromide fine grains are mixed, the development of the silver halide grains in the high-sensitivity monodispersed emulsion causes the development of other fine grains to occur rapidly. It is possible to blacken and efficiently form a variety of high-contrast colored images. For example, by using two or more emulsions in combination as described in Japanese Patent Application No. 60-64199 and Japanese Patent Application No. 60-232086. Can be done.

The Heloge/Silver Fide emulsion according to the invention may be a normal negative emulsion or a positive emulsion depending on the purpose.

In the present invention, so-called internal latent image type or internal capri type halogen/silver oxide emulsions can be used alone or in combination. For example, US Pat. No. 2,996,382,
178282, British Patent No. 1426277, Japanese Patent Publication No. 44-27065, Japanese Patent Publication No. 47-8738, etc., as well as Japanese Patent Application Publication Nos. 58-215647, 188438-1988, 1884-1987 filed by the present applicant. Silver halide emulsions described in Japanese Patent Application No. 121039, No. 61-48832, and Japanese Patent Application No. 60-93328 are used. In particular, in the case of a positive type, a direct positive type silver halide emulsion is used, and in this case, an internal latent image type silver halide emulsion that is not fogged in advance is used.

In the non-fogged internal latent image type silver halide emulsion used in the present invention, the surfaces of the silver halide grains are not pre-fogged, and the latent image is mainly formed inside the grains.
Is it an emulsion containing Rogge/silver oxide, or more specifically,
Silver halide emulsion is made into silver on a transparent support by 0.5 to 3
9/- was coated, exposed to light for a fixed time of 0.01 to 10 seconds, and developed for 5 minutes at 18°C in the following development standard A (internal type developer). The maximum f! measured by A silver halide emulsion coated with the same number as above and exposed in the same manner was treated with the following developer B (
O internal development preferably has a density that is at least 5 times greater, more preferably at least 10 times greater than the maximum density obtained when developed for 6 minutes at 20° C. in W open mold developer). Liquid A Metol 2g Sodium sulfite (anhydrous) 909 Hydroquino 7
8g Soda carbonate (-water salt) 52.59KBr
5 9 work
Add 0.59 water
II1 Surface developer B Metol 2.59 Emperor - Ascorbyya 109N! LBO□-4H20
359 KBr 1 9 Water is added to form a ltt intraclinical emulsion. Examples of such emulsions include U.S. Pat.
No. 5582, JP-A-52-156614, JP-A No. 57-7
9940 and 58-70221, and a shelled emulsion thereof, US Pat. No. 3,761,276
No. 3,850,637, No. 3,923,513, No. 4,035.185, No. 4,395,478,
4,431,730, 4,504,570, JP-A No. 53-60222, 56-22681, 5
No. 9-208540, No. 60-107641, No. 61
-3137, Japanese Patent Application No. 61-3642, Research Disclosure No. 11423510 (issued November 1983) P236, Research Disclosure A18155 (issued May 1979) i'265-268. Gold*V-doped core/shell type...Rogge/Silver Fide emulsion can be mentioned.

When the color-sensitive layer is divided into two or more layers, the layer containing the contrast enhancer and the monodispersed silver oxide emulsion according to the present invention is the most sensitive layer among the two or more color-sensitive layers. It is preferable that there is a 1% Kosho 49-15 between the high sensitivity layer and the low sensitivity layer.
No. 495! ! 4-! Intermediate! - It is preferable to provide a non-photosensitive layer, and it is especially preferable that the intermediate layer is a non-photosensitive fine grain silver halide emulsion layer as described in JP-A-59-160135.

The photographic emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are described in Research Disclosure 417643 and Research Disclosure 18716 and are summarized in Table K below. Spectral sensitization is preferably carried out by adding a sensitizing dye during the grain formation process or before chemical sensitization. In particular, in the case of internal latent scratch type silver halide emulsions, it is preferable to carry out chemical sensitization after core grain formation, chemical sensitization during or after shell formation, and spectral sensitization. For example, the method described in the specification of patent application (7) dated February 12, 1988 (applicant: Fuji Photo Film Co., Ltd.) may be used.

Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures and are listed in the table below.

1 Chemical sensitizer page 23 page 648 right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizers, pages 23-24 648 Right column ~ Super sensitizers Page 649 Right column 4 Anti-fogging agent
Pages 24-25 Page 649 right column and stabilizer 5 Light absorber, 7 Page 25-26 Page 649 right column ~ Ilter dye Page 650 left column Ultraviolet absorber 6 Anti-staining Page 25 right column Page 650 left ~ agent
Right column 7 Hardener page 26 Page 651 Left column 8
Binder page 26 Same as above 9 Plasticizer,
Lubricant page 27 650 Negative right column 10 Coating aid, surface Pages 26-27 Same as above 11 Static prevention Page 27 Same agent In addition, in the case of the color writing material of the present invention, the output light of the digital information used is e.g. laser light, LED Patent application dated February 6, 1988 and patent application (7) dated February 12, 1986 (respectively issued by Fuji Photo Film Co., Ltd.) using the spectral sensitization method described in the specification for light emission, etc. It will be done.

In the present invention, a high contrast accelerator is used in order to promote the high contrast effect of the high contrast agent or its precursor, and also to exhibit effects such as promoting the progress of development, suppressing the occurrence of capri, and stabilizing development. Particularly preferred silver halide emulsions have the following formulas -ff CIl+), (fV),
It is preferable to use a high contrast accelerator selected from compounds represented by (V) and (Vl) Itcx and compounds different from each other according to the general formula (Vl) K.

General formula (III) where R31,,32 are alkyl groups or h3i, R3
2 are connected to form a ring, and there is 10-1〉N in the ring.
R34 may be included (R34 represents an acyl group).

R33 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The groups R31, R32, and R33 may further have a substituent.

A represents an optionally substituted alkylene group.

X BarCComm-1-ocoh, -Nscos
h.

-Jlri(,:00.-Coo, -0 to t), -
GO, -NiiUO.

-8o NM-=, -NIO-, -802-t! −
0-4y is shown.

General formula (fV) where R41, R42, R43% R44 are substituted or unsubstituted alkyl groups, R41, and 42. R43
and R44 may be connected to form a region, and -0-
1> R45 may be included (R represents an acyl group)
. A represents an optionally substituted alkylene group. X4,
Y4 is amino-jli! or an alkyl-substituted amine group. z4 represents a -valent anion.

General formula (V) Here X5e represents an anion.

R” barY'-J<”,-Y'-Cook”,-
Y5-(,1cOkt”.

-Z'-000-Y'-QCORs3, -z'-oco
-y'-cookL", -Z'-Coo-X"-CvO
R” 1: Table wa f.

R52 is a hydrogen atom, a rogen atom, an alkyl group, an aryl group, an aralkyl group, an oxycarbonyl group.

Alkoxy group, alkoxy group, amino group, substituted amino group, acylamido group, sulboamide group, force.

However, R5i and R52 have at least one ester group.

General formula CM) A7Y9-R) Engineering.

In the formula, A represents a group adsorbed to silver halide. Y6
represents a divalent linking group consisting of an atom or atomic group selected from hydrogen atoms, carbon atoms, nitrogen atoms, hydrogen atoms, and sulfur atoms. R represents an organic group containing at least a thioether group, an amino group, an ammonium group, an ether group, or a heterocyclic group.

R6 is O or l1m is 1 or 2.

This will be explained in more detail in general formula (■).

Examples of mercapto compounds bonded to heterocycles include substituted or unsubstituted mercaptoazoles (e.g. 5-
Mercaptotetrazoles, 3-mercapto-1,2,
4-) Riazoles, 2-mercaptoimidazoles,
2-Mercapto-1,3,4-thiadiazoles, 5-
Mercapto-1,2,4-thiadiazoles, 2-mercapto-1,3,4-oxadiazoles, 2-mercapto-1,3,4-selenadiazoles, 2-mercaptooxazoles, 2-mercapto Thiazoles, 2-
mercaptobenzoxazoles, 2-mercaptobenzimidazoles, 2-mercaptobe/zuthiazoles, etc.), substituted or unsubstituted mercaptopyrimidines (
Examples include 2-mercaptopyrimidines and 14-mercaptopyrimidines.

Examples include triazoles, tetrazoles, azaindenes, pyrazoles, and indoles.

Hydrocarbon compounds containing mercapto compounds include alkyl mercaptans, aryl mercaptans, alkenyl mercaptans, aralkyl mercaptans, and the like.

Y represents a divalent linking group consisting of an atom or a group of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. it61, R62, R as a divalent linking group
63, R64, R68, R66, R67, R68, R6
9OyohiR is a hydrogen atom, a substituted or unsubstituted alkyl group (9+1 is an ethyl group, an ethyl group, a propyl group, a n-butyl group, etc.), a substituted or unsubstituted aryl group <fQ is a phenyl group group, 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (e.g.
proynyl group, l-methylvinyl group, etc.), or substituted or unsubstituted aralkyl group (e.g., benzyl group,
7 enethyl group.

etc.).

R is a thioether group, amino group (including salt form), ammonium group, ether group, or heterocyclic group (including salt form)'? : Respects organic groups containing at least one. Examples of such organic groups include groups selected from substituted or unsubstituted alkyl groups, alkenyl groups, aralkyl groups, or aryl groups combined with the above groups; Good too. For example, dimethylaminoethyl group, aminoethyl group, diethylaminoethyl group, dibutylaminoethyl group, diethylaminoethyl group hydrochloride, dimethylaminoethyl f5F ethyl group, 4
-dimethylaminophenyl g, 4-dimethylaminobenzyl group, methylthioethyl group, ethylthiopropyl group,
4-methylthio-3-cyanophenyl group, methylthiomethyl group, trimethylammonioethyl group, methoxyethyl group, methoxyethoxyethoxyethyl group, methoxyethelthioethyl group, 3.4-dimethoxyphenyl group, 3
-chloro-4-methoxyethyl group, morpholinoethyl group, l-iodazolylethyl group, morpholinoethylthioethyl group, pyrrolidinoethyl group, piperidinoprobyl group,
Examples thereof include 2-pyridylmethyl group, 2-(1-imidazolyl)ethylna, onityl group, pyrazolylethyl group, triazolylethyl group, and 7-ethoxycarponylaminoethyl group in methoxyethoxyethoxyethyl group. ♂ represents O or 1, - represents 1 or 2.

General Formula (Vl-1) In the general formula (Vl), Q is preferably a 5- or 6-membered heterocyclic ring composed of one type of atom, preferably carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and selenium atoms. It is expressed as a group of atoms necessary to form a sound.

The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of the heterocycle include tetrazoles, triazoles, imidazoles, thiadiazoles, oxadiazoles, selenadiazoles, oxazoles, thiazoles, benzothiazoles, benzthiazoles, benzimidazoles, Pyrimidines, etc. are affected.

M is a hydrogen atom, an alkali metal atom (for example, a sodium atom, a potassium atom, or an atom), an ammonium group (for example, a trimethylammonium group, a dimethylbenzylammonium group, etc.), or M! under alkaline conditions. ) i or a group that can be an alkali metal atom (N represents an a7thyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.).

In addition, these heterocycles include a nitro group, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a mercapto group, a cyano group,
Substituted or unsubstituted alkyl groups (e.g., methyl group, ethyl group, propyl group, t-butyl group, cyanoethyl group, etc.), aryl groups (e.g., phenyl group, 4-
Methanesulfone 7)' phenyl group, 4-methylphenyl group, 3゜4-dichlorophenyl group, naphthyl group, etc.)
, alkenyl groups (e.g. allyl group 1, etc.), aral groups (e.g. benzyl group, 4-methylbenzyl group, 7enethyl group 1, etc.), sulfonyl groups (e.g. methanesulfonyl group, ethanesulfonyl Ai, p-)luene sulfonyl group,
etc.), carbamoyl group (for example, unsubstituted carbamoyl group,
methylcarbamoyl group, phenylcarbamoyl group, etc.)
, sulfamoyl group (e.g. unsubstituted sulfamoyl group,
Methylsulfamoyl group, phenylsulfamoyl group,
etc.), carbonamide groups (N-acetamide groups, benzamide groups, etc.), sulfonamide groups (e.g. methanesulfonamide groups, benzenesulfo/amide groups, p-toluenesulfonamide groups, etc.), acyloxy groups (N-acetamide groups, benzamide groups, etc.), acyloxy groups (N-acetamide groups, benzamide groups, etc.), is an acetyloxy group, benzoyloxy group, etc.), a sulfonyloxy group (e.g. methanesulfonylethyl group, etc.)
, ureido group (for example, unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group, etc.)
.

Thiourido groups (e.g., unsubstituted thioureido groups, methylthioureido groups, etc.), acyl groups (e.g., acetyl groups, benzoyl groups, etc.), oxycarbonyl groups (e.g., methoxycarbonyl groups, cyanoxycarbonyl it, etc.)
, oxycarbonylamino group (e.g., methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxy7carbonylamino group, etc.), carboxylic acid or its salt, sulfone #It or its salt, hydroxyl group, etc. However, from the viewpoint of nucleation promoting effect, it is preferable not to be substituted with a carboxylic acid or a salt thereof, a sulfone #R or a salt thereof, or a hydroxyl group.

The heterocycle represented by Q is preferably tetrazoles, triazoles, imidazoles, thiadiazoles, and oxadiazoles.

Y, Rlm, and n each have the same meaning as in general formula (Vl).

General formula (Vl-11) In the formula, Y6, R'1m', n6, Q and M are according to the general formula (1)
Examples of heterocycles formed depending on the appearance include indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, Tetrazoles, Buto2
Examples include azaindenes, triazaindenes, diazaindenes, pyrazoles, and indal #1.

Special application 11f again! No. 161-136948 (pages 2-6 2
and pages 16-43), Japanese Patent Application No. 136949/1983 (1986-136949)
2-43), Japanese Patent Application No. 153481/1981 (10-2
9) can be mentioned.

Specific compounds represented by the general formula [VI] of the present invention are shown below, but the compounds of the present invention are not limited thereto.

(Vl-1) 3-mercapto-1,2,4-)riazolo[4,5-a)pyridine (Vl-2) 3-mercapto-1,2,4-triazolo[4,5-a)pyrimidine ( Vl-3) 5-mercapto-1,2,4-triazolo[I,5--)pyrimidine (Vt-4) 7-(2-dimethylaminoethyl)-5-
Mercapto-1,2,4-triazolo(1,5-a)pyrimidine (Till-5) 3-mercapto-7-methyl-1
,2,4-triazolo(4,5-a)pyrimidine (Vl-6) 3.6-dimercabuto 1.2.4-
) Riazolo(4,5-1)pyridazine (Vl-7) 2-mercapto-5-methylthio-1
,3,4-thiadiazole (■-8)3-mercapto-4-methyl-1,2,4-
) Riazole (■-9) 2-(3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride (Vl-10) 2-(2-morpholinoethylthio)
-5-mercapto-1,3,4-thiadiazole hydrochloride (■-11) 2-mercapto-5-methylthiomethylthio-1,3,4-thiadiazole sodium salt (■
-12) 4-(2-morpholinoethyl)-3-mercapto-1,2,4-triazole (■-13) 2-(2-(2-dimethylaminoethylthio)ethylthio]-5-mercapto-1, 3,4-
Thiadiazole salt powder General formula [u1], (IV) which is a high contrast accelerator of the present invention
The compounds represented by , (V) and (Vl) can be selected from amine compounds represented by 'C' by the general formulas [kawa], (fV) and (V) and used in the color developing solution.

The amines that can be used in the present invention include inorganic and organic amines, and organic amines include aliphatic amines, aromatic amines, cyclic amines, aliphatic-aromatic cyclic amines, and heterocyclic amines. Primary, secondary, @tertiary amine or wi
Any quaternary ammonium compound can be used.

Specifically, alkanolamines such as those described in JP-A-56-106244 (e.g., 3-diethylamino-1-propanol, 2-methylamino-1-ethanol, 2-diethylamino-1-ethanol, 5-diethylamino-1-ethanol, −
Amino-1-/Z-tanol, 1-diethylamino-2
, 3-dihydroxypropane, etc.) are also preferred.

Also, JP-A-60-140340 (32-36 true, 3
Examples include the compounds described on pages 7 to 38 and pages 40 to 44). For example, the following compound @ can be given, but the present invention is not limited thereto.

Various color couplers can be used in the present invention, specific examples of which include Sodeyama Nori Search Disclosure (
RD) 17643, ■-〇, described in the patent described in G. As dye-forming couplers, the three subtractive primary colors (i.e. yellow, magenta and cyan)!
! :The coupler provided by color development is important, and a specific example of a diffusion-resistant 4-equivalent or 2-equivalent coupler is the dD1 mentioned above.
In addition to the couplers described in Patents No. 7643.1-C2 and No. 9, the following can be preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. can be lost. A specific example of this is the US patent jJ! No. 2,407,210, No. 2.875,057
No. 3,265.506, etc. The use of two-equivalent yellow couplers is preferred for the present invention, U.S. Pat. No. 3,408,194, Id.! 3,44
7.92s, No. 3.933,501 and No. 4,022,620g, etc., or Japanese Patent Publication No. 10739/1983,
U.S. Patent No. 4,401,752 @4,326,0
No. 24, RD13053 (April 1979), British Patent No. 1.425,020, West German Application Published! 2,219,
No. 917, No. 4@2,261,361, No. 2,329
Typical examples include the nitrogen atom separation type yellow couplers described in , No. 587 and No. 2,433,812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, and a single α-benzoylacetanilide coupler can provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic indacylon- or cyanoacetyl-based couplers having a ballast group, preferably 5-pyrazolone- and pyrazoloazole-based couplers. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group in terms of the hue and color density of the coloring dye.
No. 311,082, No. 2,343,703, No. 2
．． No. 600,788, *2,908,573, *3.062,653, *3,152.896, and *3,936,015. As the leaving group for the two-pixel 5-pyrazolone coupler, the nitrogen cryo leaving group described in U.S. %*@4,310,619 or the arylthio group described in U.S. Pat. No. 4,351,897 is particularly used. KtFf is awesome. Also European patent @7
The 5-pyrazolone coupler having a ballast group described in No. 3,636 provides high color density. As a pyrazoloazole coupler.

Pyrazolobenzimidazoles as described in US Patent No. 3,369,879, preferably US LfA Patent No. 3.725
Pyrazolo (5,1-cJ(1,
2,4)) Liazoles, Research Disclosure 24220 (June 1984) and JP-A-60-3
3552 and pyrazolopyrazoles described in Research Disclosure 24230 (June 1984) and JP-A-60-43659. U.S. Patent No. 4,500,6 in terms of low yellow side absorption of the coloring dye and light fastness.
Idashi (1,2-b) pyrazoles described in No. 30 are preferred, and are European patents! Pyrazolo(1,5-1+) (1,2,4)) riazoles described in No. 119,860A are particularly preferred.

Cyan couplers that can be used in the present invention include:

Hydrophobic, diffusion-resistant naphthol-based and phenolic couplers include the 7-thol couplers described in US Pat. No. 2,474,293, preferably US rA! permission g4
, 052,212, 4,146,396, 4,228,233, and 4,296,200, two-pixel naphthol couplers that eliminate oxygen atoms are representative examples. Can be mentioned. Specific examples of phenolic couplers include U.S. Patent No. 2.369,929, U.S. Pat.
It is described in the same No. 2,895,826.

Cyan couplers that are noisy with respect to humidity and temperature are preferably used in the present invention, and a typical example thereof includes an alkyl group having a ether group or more at the meta position of the phenol nucleus described in U.S. Pat. No. 3,772,002. , 1lltt- Phenolic Thread Cyan Coupler, US Patent! 2.772,
No. 162, No. 3,758,308, @4,126
, No. 396, No. 4,334,011, No. 4,32
No. 7,173, FBA Glaze Patent Publication No. 3.329,729
No. 3,446,622, European Patent No. 121,365, etc.
3. No. 999, same! These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in Japanese Patent No. 4,451,559 and No. 4,427,767.

In order to correct unnecessary absorption of color pigments, it is preferable to perform masking by using a colored coupler in combination with a color photosensitive material for photographing. Yellow colored magenta couplers described in U.S. Pat. No. 4,163,670 and Japanese Patent Publication No. 57-39413, etc. or U.S. Pat. No. 4,004,929, No. 4,138,258 and British Patent @1,14
Typical examples include the magenta-colored cyan coupler described in No. 6,368. Other colored couplers are described in RD 17643.4-0 above.

Granularity can be improved by using a coupler whose color patch has an appropriate diffusivity. Such a coupler is
U.S. OIL Patent No. 4,366,237 and British Patent II
l! Specific examples of magenta couplers are described in No. F 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570 and West German Publication No. 3,234,533. ing.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is a U.S. patent! 3,451,82
No. 0 and No. 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2.102,173 and US I! il￥fFF＠4,
No. 367,282.

Couplers that release all photographically useful residues upon coupling can also be preferably used in the present invention. DIR coupler releasing development inhibitor kD17643.4 as mentioned above.
The patent couplers listed in Sections .-F. are useful.

Preferable in combination with the present invention is JP-A No. 1185
Development song inactivation type represented by No. 7-151944; Korean Patent No. 4,248,962 and Japanese Patent Application Laid-open No. 1542-1982
Timing type represented by No. 34; patent application 1986-396
The reaction type represented by No. 53 is preferable in terms of percentage, and the preferred ones are JP-A-57-151944 and JP-A-58-217932.
No. 59-75474, Japanese Patent Application No. 59-82214, Japanese Patent Application No. 59-82214, Japanese Patent Application No. 59-90438, etc., and the image liquid deactivation type DIM cutler described in Japanese Patent Application No. 59-39653, etc. Suitable supports that can be used in the present invention are reactive DIR couplers as described, for example, the R
D. Mu 17643 no. 28 and same, rot 18716 no. 6
It is written in the stone column on page 47 to the pressure column on page 648. In particular, the support used in the present invention is preferably a thin paper, for example, about 50 μm to 200 μm synthetic paper, an OHP film, or the like.

On the support, a night-sensitive photosensitive layer (BL), a green-sensitive photosensitive layer (
Gh), a red-sensitive layer (1 (L)), a protective layer (PL), and between the photosensitive layers, an intermediate layer (ML), a filter layer (YL), an antihalation layer (AHL), etc. are provided depending on the purpose. For example, (1) Support/Aki1J/ML/L/ML/G
L/ML/Yli''/BL/)'L(2) Support 7 A
tL/ML/BL/ul, /RL/mL/GL/mL/
Pi.

(a> Support/Ai-IL/ML/GL/Ml,
/LE/ML/YF/BL/PL etc. Each photosensitive layer can be divided into two or three or more layers and provided adjacent to each other or through other photosensitive layers. It can also be constructed with three layers including an infrared source layer. Each photosensitive layer contains the yellow coupler and magenta coupler 2-
or cyan coupler can be used.

The color photographic material according to the present invention has the above-mentioned RD, 4
17643, pages 28-29 and the same, rot 18716, 6
51 Existing damage can be treated by the usual methods described in the left column to right column.

The color photographic light-sensitive material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, white fixing or fixing treatment.

For example, it is preferable to use the nine development processing method described in the patent specification filed by the present applicant on October 31, 1986.

In the present invention, the coloring MS solution generally used for the development of color photosensitive materials preferably contains an aromatic primary amine color developing agent as a main component, and preferably has a − of 9.8 to 1.
1.5 is an alkaline aqueous solution ◎ As this color developing agent, achinophenol compounds are also useful, but p
-) Unylene diamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N,N-jethylanili7.3-1 thyl-4-amino-N-
Ru-N-β-hydroxylethylaniline, 3-methyl-4-7minor N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline 217 and their sulfates, salts, p-toluenesulfonates, and the like. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

Additionally, pH buffering agents such as alkali metal carbonates, borates or phosphorous salts, development inhibitors such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds or capri It generally contains an inhibitor. If necessary, preservatives such as sulfites, organic solvents such as triethanolamine, diethylene glycol, polyethylene glycol,
Development accelerators such as quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, tackifiers, amino acids. polycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid,
Various chelating agents such as phosphonocarboxylic acids, oxidation inhibitors described in West German Patent Application No. 2,622,950, and the like are added to the color developing solution.

In the color development process, development nuclei generated on photosensitive silver halide grains are promoted by a nucleating agent, and color development is further accelerated by a coupling reaction between the electron oxidized form of the color developing agent and the coexisting color coupler. Ru. On the other hand, the undesirable two-electron oxidized product of the color developing agent, which is formed as a by-product of K due to side reactions and air oxidation, is efficiently returned to the original color developing agent after being imaged by the oxidizing agent. In this reaction system, a trapping agent having the ability to capture the oxidized reconstituted product and return it to the original reconstituted product is coexisting. By using this restoring agent and its oxidized capture agent together, the remaining color developing agent can be preserved without interfering with the coupling color reaction. A similar reaction system has been observed in spot white development, for example, in the combination of three types of compounds: hydroxide, l-phenyl-3-pyrazolidone, and white value acid salt, but is not known in color development systems. In particular, with the invention of this reaction system, benzyl alcohol, which is a conventionally used development accelerator, can be substantially removed from the developer. "Substantially" means 2-/1 or less, more preferably α5w171 or less, most preferably not at all.

As described above, in the color development agent according to the present invention, a "restoring agent" that restores the oxidized form of the color developing agent and a "capture agent" that captures the oxidized form of the restoring agent and returns it to the original state are made to coexist. Can be done. It is defined by the mutual redox properties of the color-forming S-imaging agent, restoring agent, and capture rigid line necessary to form the above-mentioned reaction system, and can be easily defined by a certain test softening. Next, as an example of a color developing agent, 3
-Methyl-4-a-)-N-ethyl-N-(β-methanesulfonamidoethyl)aniline is used to define the method. If the crude drug used changes, just measure the number of moles together. A "restoring agent" or a "capturing agent" can be determined by the method described in the patent specification (pages 15 to 20) filed by the present applicant on October 31, 1986. Further, amines described in Japanese Patent Publication No. 56-106244 may be used.

General formula (III) in the present invention, (fV, l, (V)
The high contrast accelerator represented by It can be added to the color developing solution. The amount used is preferably 1 x 10 cells or 1 mol, preferably 1 x 1 per liquid.
0 mole to 0.5 mole.

After color development, the photographic emulsion layer is usually bleached.

The bleaching treatment may be carried out simultaneously with the fixing treatment in a one-bath white fixing process (clicks), or may be carried out separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of whitening agents used in bleaching or bleach-fixing include compounds of polyvalent metals such as iron (ill), cobalt (ill), chromium (Vl), and copper (II) (e.g., ferricyanide), and peracids. , quinones, nitroso compounds; dichromium salt; iron (Ill)
or organic complex salts of Conol (11) (e.g. complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, acinopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or citric acid, Organic acids such as tartaric acid, phosphorus/acupuncture; persulfates; hydrogen peroxide; permanganates and the like can be used. Among these, organic complex salts and persulfates of iron(1) are preferable from the viewpoint of rapid processing and environmental pollution. Iron (I
The salts of aminopolycarboxylic acids or aminopolyphosphones useful for forming the organic complex salts of II) are as follows: ethylenediamine 1.1 acid, diethylenetriaminepentaacetic acid.

Ethylenediamine-N-(β-oxyethyl)-N,N
', N/-triacetic acid, 1.2-diaminopronotetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1.3- Diamino-2-propaturic acid, methyliminodiacetic acid, iminodiacetic acid.

Hydroxyliminoniacetic acid, dihydroxyethylglycine ethyl ether diamine tetraacetic acid, / +7 call ether diamine tetraacetic acid.

ethylenediaminetetrapropionic acid, ethylenediaminenipropionacetic acid, phenylenediaminetetraacetic acid, 2-phosphonobutane-1,2,4-triacetic acid.

1.3-diaminopropanol-111,111. j4
',N'-tetramethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylsinphosphonic acid, 1,3-pro♂diamine-N,N,N',N'-tetramethylenephosphonic acid Acid, 1-hydroxyethylidene-1,1'-diphosphonic acid.

etc. can be mentioned.

Among these compounds, iron(III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,2-cyanopropanetetraacetic acid, and methyliminodiacetic acid are preferred because they have a high yield.

As the iron(1) complex salt, one or more types of ready-made complex salts may be used, or iron(1) salts (e.g. #1 ferric sulfate, ferric chloride) may be used.
Iron, nitrate #l ferric, ferric ammonium sulfate, phosphorus [
A ferric ion complex salt may be obtained by reacting a chelating agent (aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.) with a chelating agent (aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.) in a solution. When forming a complex salt in a solution, one or both of the ferric salt and the intermediate rate agent may be used in combination. In either case of forming a pre-formed complex salt or forming a complex salt, the chelating agent may be used in an amount greater than the stoichiometric amount. In addition, the bleaching solution or bleach-fixing solution containing the above @2 iron ion complex contains metal ions other than iron such as calcium, magnesium, aluminum, nickel, bismuth, zinc, tungsten, cobalt, copper, complex salts thereof, or hydrogen peroxide. may be included.

Persulfates for bleaching or bleach-fixing that can be used in the present invention include alkali metal persulfates such as potassium persulfate and sodium persulfate, or ammonium persulfate.

The bleach or bleach-fix solution may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. iodine). (ammonium chloride) rehalogenating agents. Boric acid if necessary,
Borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. More than 1 types of inorganic acids and organic acids with buffering capacity Also, alkali metal or ammonium salts thereof or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The amount of bleaching agent in bleaching solution 11 is suitably 0.1 to 2 mol, and a preferable range of the bleaching solution is 0.5 to 8.0 mol in the case of ferric ion complex salt, especially amino acid. polcarboxylic acid,
In the case of ferric ion complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid, it is 4.0 to 7.0. In the case of persulfate, at a concentration of α1 to 2 mol/l... is 1
The range of 5 to 5 is preferable.

The fixing agents used for fixing or bleach-fixing are all known fixing agents, namely thiosulfates such as sodium thiosulfate, ammonium thiosulfate; thiocyanates such as sodium thiocyanate, ammonium thiocyanate; ethylene bisthioglycolic acid, 3 A water-soluble silver halide solubilizing agent such as a thioether compound such as .6-cythia-1,8-octanediol or thioureas can be used alone or in combination of two or more thereof. Furthermore, in the bleach-fixing process, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used.

For fixing or bleach-fixing processing, the fixer concentration is 0, 2~
4 mol/l is desirable. In addition, in the bleach-fixing process,
iI white fixing 11 [1j! Akushi, ferric ion complex salt is 0
．． The amount of the fixing agent is preferably 1 to 2 moles, and the fixing agent is preferably in the range of 0.2 to 4 moles. In addition, - of fixing and bleach-fixing solutions is usually 4.0 to 9.
．． 0 is preferable, and 560 to 8.0 is particularly preferable.

The fixer g or bleach-fix solution may contain: *In addition to the above-mentioned additives that can be added to the white liquor, preservatives such as sulfites (e.g. sodium sulfite, IP potassium sulfate, ammonium sulfite), bisulfites, hydroxylamine, Hydrazine, a bisulfite adduct of an aldehyde compound (for example, acetaldehyde sodium bisulfite), etc. can be contained. Furthermore, various fluorescent brighteners, antifoaming agents, surfactants, polyvinyl♂rolidone, organic solvents such as methanol, etc. can be contained.

Bleach enemies, bleach-fix solutions and their pre-baths.

A bleach accelerator can be used if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A No. 53-32736, No. 53-57831, No. 374
No. 18, No. 53-65732, No. 53-72623, No. 53-95630.

No. 53-95631, No. 53-104232.

Compounds having a mercapto group and a disulfide group as described in JP-A Nos. 53-124424, 53-141623, 53-28426, and Research Disclosure No. 17129 (July 1978);
Thiazolidine derivatives as described in Japanese Patent Publication No. 140129;
No. 0832, No. 53-32735, US Patent No. 1! 3
, 706,561; Iodides described in West German Patent No. 1J27,715 and JP-A-58-16235; West German Patent No. 966.410 and JP-A No. 2,74
Polyethylene oxides described in Japanese Patent Publication No. 8,430; boriaone compounds described in Japanese Patent Publication No. 45-8836; and other Japanese Patent Publications Nos. 49-42434, 49-59644, 53-9/4927, 54-35727 No. 55
Compounds described in No. 26506 and No. 58-163940 and iodine and bromine ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferable because they have a large promoting effect at a warm temperature, and are particularly preferred as described in US Patent No. 3.89.
Preferred are the compounds described in No. 3.8573, West German Patent No. 1,290,812, and JP-A-53-95630. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators can be washed even if added to the photosensitive material.

Fixer S or bleach-fixing process? lkK is generally subjected to processing steps such as water washing and stabilization.

Various known compounds may be added to the water washing process and stabilization treatment for the purpose of preventing precipitation and stabilizing the washing water (e.g., inorganic phosphoric acid, aminopolycarbonate, organic phosphorus, etc.) medium-rate agents, bactericides and anti-inflammatory agents that prevent the growth of various bacteria, algae, and molds (e.g., J. Antibacterial and Antifungal Agents).
fung, Agents) Ma01.11.45t
p 207-223 (1983) K and compounds described in Hiroshi Horiguchi 11 @ Chemistry of antibacterial control), metal salts, alkali metals and ammonium salts represented by magnesium salts, aluminum salts, bismuth salts, etc. Alternatively, surfactants, etc. can be added as necessary to prevent drying load and unevenness.Also, waist wear Photographic Science & Zy
Genial/gu magazines (Photo, Sai, jEng,
), 6th Lane e344-359 (1965)
You may add the compound described in etc. 4? It is effective to add chelating agents and l11m anti-bacterial agents.

The water washing process is a multistage countercurrent water washing of 24 W or more (for example, 2 to 9
It is common practice to reduce the amount of water used for washing by using a tank. Furthermore, a multi-stage countercurrent stabilization treatment process as described in JP-A No. 57-8543 may be performed on the rinsing process. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing the image quality. For example, membrane ri4t-adjust (e.g. pH 3-9) various buffers (e.g. borax salts, metaborous eIR salts, borax, phosphates, carbonates,
Representative examples include potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants,
Various additives such as anti-piping agents (thiazole type, isothiazole type, halogenated phenol, sul7anilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, hardener metal salts, etc. may be used. , two or more of the same or different desired compounds may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

In addition, the post-fixing (washing-stabilization) process that is normally carried out in color photosensitive materials for photography can be replaced with the above-mentioned stabilization process and water-washing process (water-saving treatment). At this time, if the magenta coupler is 2-color, the formalin in the stabilizing bath may be removed. The washing and stabilization processing time of the present invention varies depending on the type of photosensitive material and processing conditions, but is usually 20 The time is from seconds to 10 minutes, preferably from 20 seconds to 5 minutes.

Various treatment liquids in the present invention are used at 10°C to 50°C. The standard temperature is 33°C to 38°C, but it is recommended to use a higher temperature to accelerate the processing and shorten the processing time.
Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, West German Patent No. 2,226,770 or US Pat. lPatent No. 3
, 674,499 or U.S. Pat. No. 3,923,
A one-bath development, bleach-fixing treatment as described in No. 511 may be performed.

In addition, each processing time can be shortened from the standard time within a reasonable range, if necessary, in order to speed up the process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent or a precursor thereof for the purpose of simplifying and speeding up processing. Precursors are preferable for inclusion in the light-sensitive material because they increase the stability of the photosensitive material. Specific examples of current drug precursors include, for example, U.S. Patent No. 3.
, 342,597, Research Disclosure No. 14850 (August 1976), and Research Disclosure No. 15159.
(November 1976), aldol compounds described in No. 13924, US I! g Metal salt complex described in Patent No. 3,719,492, JP-A-53-
Urethane compounds described in No. 135628, JP-A-56-6235, JP-A-56-16133, JP-A-56-5
No. 9232.

No. 56-67842, No. 56-83734, No. 56
No.-83735, No. 56-83736.

No. 56-89735, No. 56-81837, No. 56
-54430, 56-106241, 56-1
No. 07236, No. 57-97531 and No. 57-8
Various salt-type precursors described in No. 3565 and the like can also be used in the present invention.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to promote color development. Typical compound Fi JP-A-56-
No. 64339, No. 57-144547, No. 57-21
No. 1147, No. 58-50532, No. 58-5053
No. 6, No. 58-50533, No. 58-50534,
It is described in No. 58-50535 and No. 58-115438.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

Each treatment bath may be equipped with heaters, temperature sensors, liquid level sensors, circulation pumps, filters, various floaters, various squeegees, etc., as necessary.

When the light-sensitive material of the present invention is a color photographic material, it can be bleach-fixed if necessary, and even when it is a color photographic material for photographing.

Example-1 Preparation method of polydisperse emulsion Silver nitrate aqueous solution, alkali halide aqueous solution, gelatin aqueous solution and excess halide were added in advance and allowed to drop naturally into a reaction pot kept at 60°C. ) and an aqueous magnesium sulfate solution, precipitated and desalted, and added gelatin to give a pAg of 7.8.
e...6.0 emulsion was obtained.

Furthermore, chemical ripening was performed using sodium thiosulfate, chloroauric acid, and rhodan ammonium, and 4-hydroxy-6-
Methyl-1,3,3a,7-chitrazainde/,1-methylureido y4. Two tw-5-mercaptotetrazole and 6-nitrobe/timigsol were added, and then gelatin was added to obtain polydisperse silver iodobromide emulsion 1. Then, the average particle diameter F (μ) and particle size distribution l were changed by varying the addition time of silver iodide morch, silver nitrate aqueous solution, and algahalite aqueous solution by changing the %ride composition of Algaf Nride to t. Dispersity B/″rf Am. The desired sensitivity was achieved by changing the chemical ripening time.

Preparation method of monodisperse emulsion according to the present invention Into a reaction vessel, in which potassium iodide and an aqueous gelatin solution are charged in advance, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution are added while automatically controlling pAg and... It was added in proportion to the increase in surface area during the growth of all particles. Next, Demol N aqueous solution (manufactured by Kako Atlas Co., Ltd.) and magnesium sulfate aqueous gold solution were added to precipitate and desalt, gelatin was added, and the pA
Emulsions of g7.8 and -6.0 were excellent.

Furthermore, thiosulfated sodium chloride, chloroauric acid and rhodan ammonium were added, and all chemical ripening was carried out, 4-hydroxy-6
-Methyl-1,3,3a,7-chitrazai/f'y,l
-Methylureidophenyl-5-mercaptotetrazole and 6-nitrobe/tuimidazole were added, and gelatin was further added to obtain a monodisperse silver iodobromide emulsion.

By changing the ratio of potassium iodide and potassium bromide in and \, the silver iodide mole St- can be changed, and the particle size can be changed by changing the amounts of ammonia aqueous solution, ammoniacal silver nitrate, and potassium halide. Ta. The chemical ripening time was varied to achieve a desired effect.

A red photosensitive layer (RL) is formed by sequentially forming layers from the support side on a film support made of transparent Naborieterentele 7 tallate.
? I got it.

A layer of the following composition was provided.

1st layer (AH) Black colloidal silver ・・・・・・・・・・・・・・・・・・
...α2V is gelatin ...
・・・・・・・・・・・・・・・-109/fi” Ultraviolet absorber UV-1・・・・・・・・・・・・α2
9/? jl” Dispersion oil O engineering L-1・・・・・・・・・
...-0,0297 m'' Second layer (ML) Ultrafine grain silver bromide agent was used.

Fine grain silver bromide (7; α07μ)・・・・・・ α
159/rll-” Gelatin ・・・・・・・・・
・・・・・・・・・・・・・・・・・・ LO9/ is the third
Layer (RL-u) A silver iodobromide emulsion was dispersed and sensitized by mixing sensitizing dyestuff and B, and then mixed with coupler C-L2.3.4.5 and coupler C-17, which will be described later, and dispersed in oil 0IL. -1 and 20 mixtures were dispersed and mixed to obtain the following composition.

Silver iodobromide emulsion A (2 mol-1rα3μS/r=α
33) (Silver) ・・・・・・・・・・・・・・・ 0.
797m” gelatin ・・・・・・・・・・・・・・・
・・・・・・・・・・・・ α9g/-sensitizing dye
・・・・・・・・・・・・・・-toxxf'%/
/A98 sensitizing dye B ・・・・・・・・・・・・・・・
...zo
・・・・・・・・・・・・・・・・・・・・・ α
3g/♂Coupler c-2・・・・・・・・・・・・・・・
・・・・・・・・・・・・α3V is coupler C-3・
・・・・・・・・・・・・・・・・・・・・・・・・
・0.2971%” coupler C-4・・・・・・・・・
・・・・・・・・・・・・・・・・・・αOIV is coupler c-5・・・・・・・・・・・・・・・・・・・・・
......O,Of 9fi” coupler C-17・
・・・・・・・・・・・・Mountain・・・・・・・・・・・・0
．． 029/ is dispersed oil O-engine L-1...
・・・・・・・・・α19/m” Dispersion oil O-engine L-2
・・・・・・・・・・・・・・・・・・0.19/m”
Fourth Layer (RL-Q) The next layer was provided using the same procedure as in 1I.

Monodispersed silver iodobromide emulsion B according to the present invention (silver) 1.
OVm” (knee 5 every ruti, yo, rμ le σ-0.08
) Gelatin ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・109/l” Sensitizing dye A
・・・・・・・・・・・・・・・・・・3X10-
'Morph' AS) Mol m-sensitive dye B ・・・・・・・・・
・・・・・・・・・ 2X10' mole/A9 mole turnip? -C-1・・・・・・・・・・・・・・・・・・
・・・・・・α019/m”Cub?-C-2・・・・
・・・・・・・・・・・・・・・・・・・・・α0
59/m” coupler c-3...2...
・・・・・・・・・・・・・・・αo3 and fake 3 coupler C
-6・・・・・・・・・・・・・・・・・・・・・・・・
...α029/711" coupler c-7...
・・・・・・・・・・・・・・・・・・・・・α02
9/Ka 3 coupler c-B・・・・・・・・・・・・・・・
・・・・・・・・・・・・α029fi” coupler〇-17・−・−・・・・−・−−−−−・−・0.00
797m” Dispersion oil O-engine L-2・・・・・・・・・・
...0.1 S) 7m" 5th layer (ML) Compound A was dispersed in an aqueous gelatin solution using a dispersion oil GMC.

Gelatin ・・・・・・・・・・・・ Old・・・・・・
...Gan 109/ is compound A ...River...
......Yamakawa...0.05g/-Dispersion oil 0 engineering L-2......0.
059/m" Sample 1 was obtained in this way. Next, coupler C-17, which is the contrast enhancer precursor of the present invention, was removed from the third layer (RL-U) and the fourth layer (RL-0). Comparative sample a was obtained in the same manner as sample-1 in other respects.

Sensitizing dye human (c1i2)3so, 7 (CH2)3So3
Na sensitizing dye B coupler c-1 coupler c-3 H coupler c-4 coupler G-5 coupler C-6 coupler C-7 coupler C-g coupler C-17 Dispersion oil 0IL-1 Dispersion oil 0IL-2 Ultraviolet absorption Agent UV-1 Compound Cpd A Filler's color temperature 4800 using tungsten light source
Gradation exposure was performed using a red filter at a temperature of ''', and the following development process was performed.

Color development (38℃) Bleaching for 3 minutes and 15 seconds Washing with water for 6 minutes and 30 seconds
Fixed for 2 minutes and 10 seconds
Washing with water for 4 minutes and 20 seconds Stability for 3 minutes and 15 seconds 1 minute and 05 seconds The composition of the saturated solution used in each step was as follows.

<Color developer> Diethylenetotaamine five vinegar a! LO91
-Human tetraxyethylidene-1゜l-diphosphonic acid 109 Sodium sulfite 4.0g Potassium carbonate
Potassium 3αOg^
L49 Potassium iodide 131
11P human gastric xyluan sulfate 1494-
(N-Ethyl-N-β-hydroxyethyl az))-2- Methyl phosphorus sulfate 4.5g Add water LOjpHxα0 <Bleach solution> Ferric ammonium ethylenediaminetetraacetate 10αOg disodium ethylenediaminetetraacetate Salt 1αOg ammonium bromide 150. Add 1αOg of nitric acid and water
1. OJ Voice 6.0 Fixer> Ethylenediaminetetraacetic acid disodium salt LO9 Sodium sulfite 409 Ammonium thiosulfate aqueous solution (70 t) 175.0d Sodium bisulfite 4.69 Add water
tozHa6 Stabilizer> Formalin (40cm) ZO++IJ
Polyoxyethylene-armonononylphenyl ether (average degree of polymerization 10) α Add 3g water and to! The obtained characteristic curve is shown in FIG.

It can be seen that curve-1 obtained from sample-1 according to the present invention is significantly harder than curve a obtained from comparative sample a (r=&5).

In this example, C-17 may be replaced with C-18 described below, or I-(1) of the above compound number.

I-(5), II-cixt II-α fathom, ■-(
c), ■-1), ■-(to) The use of O compounds also had the effect of creating both stations.

Example 2 The fifth layer (MC) was prepared according to the method of Example-1 Sample-1.
I got it in 4. On top of that, the following layers were provided in the same manner.

6th layer (GL-u) Monodisperse silver iodobromide emulsion according to the present invention Monodisperse silver iodobromide emulsion according to the present invention Gelatin
......LO9μ8 sensitizing dye C...
・・・・・・・・・・・・・・・3×1O-1i-/
/A9 mole sensitizing dye D・・・・・・・・・・・・・・・
... 2x10 moVA9 mole coupler C-10・
・・・・・・・・・・・・・・・・・・・・・・・・ 0
．． 49/s” coupler C-11・・・・・・・・・・
・・・・・・・・・・・・・・・ 0.197n” coupler C-12・・・・・・・・・・・・・・・・・・
...0.02Vn" Cub Two C-18...
・・・・・・・・・・・・・・・・・・・・・0.029
iψ dispersion oil 0IL-2・・・・・・・・・・・・・
...0.059im" 7th layer (GL-0) Polydispersed silver iodobromide emulsion (7 mol ratio, RO, 8B S
/7'=α29) 0.99/7jL"
Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.9 to 8 sensitizing dye C・
・・・・・・・・・－・・・・・・ 2x10 mower/A9
Molar sensitizing dye D ・・・・・・・・・・・・・・・ L
5X10 mo//A9 mole coupler C-12...
・・・・・・・・・・・・・・・・・・ α08g/♂ Coupler C-14・・・・・・・・・・・・・・・・・・・
...α059f-Cab2 C-18...
・・・・・・・・・・・・ α003g/n&”Dispersion oil 0IL-1・・・・・・・・・・・・・・・
α089/l" Dispersion oil 0 engineering L-1...
・・・・・・・・・α039,4” 8th layer (MC) Seratin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・ L29/m” Compound A ・・
・・・・・・・・・・・・・・・・・・・・・・・・
... α6 Shiga 8 dispersion oil O engineering L-1...
・・・・・・・・・ α39/L” 9th layer (YFL) Yellow colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・α29/-gelatin ・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 0.89
im” Compound A ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ α29il'' Dispersion oil 0IL-1・・・・・・・・・・・・ α19
fi” 10th layer (BL-u) Monodispersed silver iodobromide emulsion according to the present invention (I-6-e %, To, aa S/a=o, iz)
g 0.29/FIL" Monodispersed silver iodobromide emulsion according to the present invention (5 molt, ?" 0.6μ 57y=α09)F
α49μm gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・109/
♂Sensitizing dye E ・・・・・・・・・・・・・・・・・・
1×10 mo VA9 mole sensitizing dye F・・・・・・・・・
・・・・・・・・・1×10 mo)/A9 mole coupler C-15・・・・・・・・・・・・・・・・・・
...0.99im"C-18 according to the present invention...
・・・・・・・・・・・・・・・・・・・・・ α0
29im” Dispersion oil 0 engineering L-3・・・・・・・・・・
・・・・・・・・・ 0.01υ侃3 11th M (BL-
0) Monodispersed silver iodobromide emulsion according to the present invention (technique: 8 molten, 7156 μs/A=O, OS, Heiko grain) G Gelatin・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ α5gΔ-sensitizing dye E ・
・・・・・・・・・・・・・・・・・・5×10-5 moV
A9 molar sensitizing dye F・・・・・・・・・・・・・・・・・・
5 x 10'''5 motb/19 mole coupler C-15.
・・・・・・・・・・・・・・・・・・・・・・・・0.
59/Fl" C-18 according to the present invention...
・・・・・・・・・・・・0.019/i” Dispersion oil 0IL-a ・・・・・・・・・・・・・・・ 0
．． 019μm 12th layer (pc-1) Gelatin・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 0.59/m' Turnip? −
C-16・・・・・・・・・・・・・・・・・・
... 0.5 g, xm" Ultraviolet absorber UV-2...
・・・・・・・・・・・・・・・ 0.1 9/m”
Ultraviolet absorber try-3・・・・・・・・・・・・・
・・・・・・ 0.1 9/IIL” Dispersion oil 0ml
-4・・・・・・・・・・・・・・・ 0.019/”
13th layer (PC-2) Ultrafine grain silver iodobromide emulsion (5 molar ratio, To, orμ
) ・・・・・・・・・・・・・・・・・・・・・
・・α2H/-gelatin polymethyl methacrylate particles (?L5μ) ・・・・・・・・・・・・・・・・・・
.....alpha.29/m" Formaldehyde scavenger 8-1...0.69/m" In addition, surfactant W-1 and hardening agent H-1 were added. Sample-2 was obtained in this way.

In addition, in the same manner as comparative sample a, up to the fifth layer was provided, and furthermore, the sixth layer (GL-u), the seventh layer (GL-0), and the tenth layer (B
From the 11th layer (BL-0) and the 11th layer (BL-0), turnip ? A comparative sample was obtained in the same manner as Sample-2 except for -C-18.

Sensitizing dye C Sensitizing dye Sensitizing dye E Sensitizing dye F Coupler C-10 Coupler C-11 Coupler C-sej Coupler C-15 Kabutsu G-16 0CR3 Kabutsu C-18 Surfactant W-1 Formalin scaven Jar-S-1 Dispersion oil 0 engineering L-3 Dispersion oil 0IL-4 (1oo-C, H□, 0-qP x O ultraviolet absorber U
V-2 Ultraviolet absorber UV-3 Hardener H-1 1,4-bis(vinylsulfone acedooxide) ethane Using a tungsten light source, Filler's color temperature 4800
Color separation was performed using a red filter, a green filter, and a blue filter at a color temperature of 20cm, and the film was exposed to 20cm, 5° microsecond steps, and developed at 0G in the same manner as in Example 1.

The obtained characteristic curve is shown in FIG.

It can be seen that the curve M-2 obtained from the sample-2 according to the present invention is significantly harder (r=10) than the curve obtained from the comparative sample. Song *-2-1 and curve-'b-1 are /
Curve-2 is calculated based on the lean filter concentration.
-2 and curve -b-2 were determined by blue filter density.

Example 3 Emulsion H An aqueous solution of potassium bromide and an aqueous solution of vitrified scissors were carefully stirred into an aqueous gelatin solution to which 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione was added per mole of A9. At the same time, they were added simultaneously at 75° C. over about 20 minutes to obtain an octahedral monodisperse silver bromide emulsion with an average grain size of only 0.4 μm. A chemical sensitization treatment was carried out by adding sodium thiosulfate and chloroauric acid (tetrahydrate) in an amount of 6 caps per mole of silver to this emulsion and heating it at 75° C. for 80 minutes. Using the thus obtained silver bromide particles as cores, they were further grown by further treatment for 40 minutes in the same precipitation environment as the first time, and finally octahedral monodisperse core/shell bromide with an average particle size of 0.7 μm was produced. A silver emulsion was obtained. After washing with water and desalting, sodium thiosulfate and chloroauric acid (tetrahydrate) were added to the emulsion in an amount of L511II per mole of silver, and the emulsion was heated at 60°C for 60 minutes to perform chemical sensitization treatment. Silver Fide Emulsion H was obtained. The core/shell silver bromide molar ratio was 0.

A full multilayer photographic paper having the layer structure shown in Table 1 was prepared using core/shell type internal latent image emulsion H on a paper support laminated on both sides with polyethylene.

The coating solution was prepared as follows.

1st layer liquid preparation nitrogen coupler (C-19) 109
and color image stabilizers UV-1 and trv-2 in a molar ratio of 4:3.
Mix 3g of L with 10m of ethyl acetate and 24d of O
was added and dissolved, and this solution was emulsified and dispersed in 90 g of a 10% aqueous gelatin solution containing 5 d of sodium decyl inzenesulfonate. On the other hand, the above-mentioned silver halide emulsion H (
A97097 contains 9) and sensitizing dye B to silver halide 1
A red-sensitive emulsion 909 was prepared by adding 2.0 x 10 moles of D on a mole basis. The emulsified dispersion, the emulsion, and the development accelerator 2-sulfo-5-interdecyl-hyrroquinone were mixed and dissolved, the concentration was adjusted with gelatin so that the composition shown in Table 1 was obtained, and the contrast enhancer n-(53 per mole of A92
A coating solution for the first layer was prepared by adding 10-' mol of JX and 45 x 10-4 mol of contrast enhancement promoter VI-9 per 191 mol.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. 1-oxy-3 as gelatin hardening agent in each layer
, 5-cyclo-triazine sodium salt was used.

Using the obtained sample-3, perform the following procedure. ) was measured. A 3200@H light source was obtained by passing a color temperature correction filter through a tungsten light source. Red filter on this
Zoo C using , green filter, and blue filter, respectively.
Color separation exposure was performed for M, , , seconds.

The following color development process was performed to obtain a high-contrast color image. The obtained image has extremely high contrast with r of about 11, and N1
The cut on the leg of 1I was a more positive color image. Although the graininess was somewhat coarse, it was advantageous for increasing the edge contrast of line drawings and halftone dots.

Even when III-(1) used in the color developing solution was used in place of IV-(1) and V-(2) by combining the molar numbers, a similar effect of maintaining high contrast was obtained.

Green-sensitive emulsion layer Sensitizing dye Blue-sensitive emulsion layer Sensitizing dye F Coupler C-19 Coupler C-21 Iis Color image stabilizer α Color image stabilizer b Color image stabilizer C Color development 1 minute 40 seconds 38°C 350d Bleach fixing 1 minute 35℃ 200d water washing ■
20 seconds 33℃ -Washing ■
20 seconds 33℃ - Wash ■ 20 seconds 33℃ 20〇 - Dry 45 seconds 75℃ - The method of replenishing the washing bath is to replenish the washing bath ■, and lead the overflow liquid from the washing bath ■ to the washing bath ■. Direct the overflow liquid from the washing bath ■ to the washing bath ■.
The so-called countercurrent replenishment method was used.

Color developer mother solution replenisher diethylenetriaminepentaacetic acid 19 2. ．． 09 diethyl human 9
0xylamine 1709 3.569N,N
Trimethyl-ethylenediamine 5. BO95,80
g Compound 1[1-(1) 4.009
4.509 Sodium Bromide 0.26
1) -Sodium chloride 3.20
9 - Potassium carbonate 259
309 Fluorescent brightener (Stilbene type) 1.09
159 Bleach-fix solution Mother solution Replenisher Ammonium thiosulfate 110g Sodium bisulfite same as mother liquor 10g Ferric ethylenediaminetetraacetic acid 409 Ammonium l hydrate Ethylenediaminetetraacetic acid 5g Disodium t2 hydrate pH 6,5 1-Hydroxyethylidene 1, 1'-diphospho4 (60
h) 1.69 bismuth chloride
0.35g polyvinylpyrrolidone
0.25g ammonia water
2.5d nitrilotriacetic acid/3Na
LO95-Chloro-2-methyl-4-isothiazolin-3-one 5011q2-octyl-4-thiazolin-3-one 50 1FIF fluorescent brightener (
4,4'-diaminostilbear series) 1.0
9pH7.5 Adjust the tone with potassium hydroxide or hydrochloric acid.

The concentrations of calcium ions and magnesium ions in the washing solution were as follows.

Magnesium ion 10181/1 Calcium ion 50117/1 Washing liquid B■～■ Tap water was mixed with H-type strongly acidic cation exchange resin (Mitsubishi Kasei Corporation)
After passing water through a mixed bed column packed with Diaion 5K-IB) and OH-type strong basic anion exchange resin (Diaion 5A-IOA) to obtain the following water quality, inocyanur dichloride was added as a disinfectant. Sodium acid V'l was added.

Calcium ion L1yxi/1 Magnesium ion 0.51111/1pH
6,9 (Effects of the Invention) By using the color recording material of the present invention, from an original composed of an image composed of line drawings, halftone dots, etc.,
You can make hard copies with excellent image quality in terms of hue, image sharpness, and edge sharpness, and a rich variety of gradations. Furthermore, the above-mentioned excellent hard copies can be made by digital output from digital software information.

[Brief explanation of the drawing]

FIG. 1 shows characteristic curves obtained with Sample 1 obtained in Example 1 and Comparative Sample a. FIG. 2 shows characteristic curves obtained for Sample 2 obtained in Example 2 and a comparative sample. Procedural amendment October 9, 1986

Claims (1)

[Scope of Claims] (1) A color recording material comprising a photosensitive layer containing a photosensitive silver halide emulsion and a color coupler on a support, in which a color having a maximum γ value of 3 or more is produced by color development. A color recording material characterized by containing a contrast-enhancing agent or a contrast-enhancing agent precursor capable of forming an image. (2) The color recording material according to claim (1), wherein the contrast enhancing agent or the contrast enhancing agent precursor is a compound represented by the following general formulas (I) and (II). General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. R^1 is an aliphatic group, and R^2 is a hydrogen atom, an aliphatic group, or an aromatic group. R^1 and R^2
may be substituted with a substituent. However, R^1, R^
At least one of the groups represented by 2 and Z^1 contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R^1 and R^2 form a 6-membered ring, and dihydro Forms a pyridinium skeleton. Further R
At least one of the substituents of ^1, R^2 and Z^1 may have X^1-(L^1)-_(m^1). Here, X^1 is a group adsorbed to silver halide or a group capable of reacting with and leaving off an oxidized product of a color developing agent. L^1 is a divalent linking group. Y^1 is a counter ion for charge balance, n^1 is 0 or 1, and m
^1 is 0 or 1. ) Or general formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^2^1 represents an aliphatic group, aromatic group, or heterocyclic group; R^2^2 is hydrogen represents an atom, alkyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, or amino group; G represents a carbonyl group, sulfonyl group, sulfoxy group, phosphoryl group, or iminomethylene group (▲ mathematical formula, chemical formula, table, etc.) ▼), and at least one of R^2^1 and R^2^2 is,
May contain ▲mathematical formulas, chemical formulas, tables, etc.▼. X
^2, L^2, m^2 are each X^ of the general formula [I]
It is synonymous with 1, L^1, and m^1. R^2^3 and R^2^4 are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group. However, a hydrazone structure (▲numerical formula, chemical formula, table, etc. available▼) may be formed by including G, R^2^3, R^2^4, and hydrazine nitrogen. Further, the groups described above may be substituted with a substituent if possible. ) (3) The following general formula [III], [IV], [V] or [VI]
The color recording material according to item (1) or item (2), characterized in that it contains a high contrast promoter represented by: General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^3^1 and R^3^2 are alkyl groups or R
^3^1 and R^3^2 may be connected to form a ring,
-O-, ▲numerical formula, chemical formula, table, etc.▼ may be included in the ring (R^3^4 represents an acyl group). R^3
^3 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The groups R^3^1, R^3^2, and R^3^3 may further have a substituent. A^3 represents an optionally substituted alkylene group. X^3 is -CONH-, -OCONH-, -NHCON
H-, -NHCOO-, -OCO-, -CO-, -NH
CO-, -SO_2NH-, -NHSO_2-, -SO
_2- or -O- group. ) General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^4^1, R^4^2, R^4^3, R^4
^4 is a substituted or unsubstituted alkyl group or R^4^
1. R^4^2, R^4^3, and R^4^4 may be connected to form a ring, and the ring includes -O-, ▲numeric formula, chemical formula, table, etc.▼ (R^4^5 represents an acyl group). A^4 represents an optionally substituted alkylene group. X^4 and Y^4 represent an amino group or an alkyl-substituted amino group. Z^4 represents a monovalent anion. ) General formula [V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X^5^■ represents an anion. R^5^1 is -Y^5-R^5^3, -Y ^5-COO
R^5^3, -Y^5-OCOR^5^3, -Z^5-
COO-Y^5-OCOR^5^3, -Z^5-OCO
-Y^5-COOR^5^3, -Z^5-COO-Y^
Represents 5-COOR^5^3. [Here, Y^5 represents an alkylene group, an arylene group, an alkylene group, and R^5^3 represents an alkyl group, an aryl group, an aralkyl group, or ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲a mathematical formula, a chemical formula,
There are tables etc. ▼ Represents. Note that R^5^4 represents an alkyl group, an aryl group, or an aralkyl group. Z^5 represents a single bond, an alkylene group, an arylene group, or an aralkylene group. ] R^5^2 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an oxycarbonyl group, an acyloxy group, an alkoxy group, an amino group, a substituted amino group, an acylamido group, a sulfamide group, a carbamoyl group, ▲Math. , chemical formula, table, etc. ▼ or represents R^5^1. However, R^5^1 and R^5^2 have at least one ester group. ) General formula [VI] A-[-(Y^6)_^6-R^6^0]_m^6 (wherein A^6 represents a group adsorbed to silver halide.Y^
6 represents a divalent linking group consisting of an atom or a group of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. R^6^0 represents an organic group containing at least a thioether group, an amino group, an ammonium group, an ether group, or a heterocyclic group. n^6 represents 0 or 1, and m^6 represents 1 or 2. )
(4) The photosensitive silver halide emulsion has a coefficient of variation S/F regarding the grain size of photosensitive silver halide grains (here, S is the standard deviation regarding the grain size, and F represents the average grain size) of 0.25. A color recording material according to any one of claims (1) to (3), which contains at least one monodispersed emulsion having the following particle size distribution. (5) A high contrast agent or high contrast agent precursor that contains a photosensitive layer containing a photosensitive silver halide emulsion and a color coupler on a support, and is capable of forming a color image with a maximum γ value of 3 or more by color development. 1. A color image forming method, which comprises color-developing a color recording material containing a color recording material in the presence of a high contrast promoter represented by the following general formula [III], [IV], [V] or [VI]. General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^3^1 and R^3^2 are alkyl groups or R
^3^1 and R^3^2 may be connected to form a ring,
-O-, ▲numerical formula, chemical formula, table, etc.▼ may be included in the ring (R^3^4 represents an acyl group). R^3
^3 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The groups R^3^1, R^3^2, and R^3^3 may further have a substituent. A^3 represents an optionally substituted alkylene group. X^3 is -CONH-, -OCON
H-, -NHCONH-, -NHCOO-, -COO-
, -OCO-, -CO-, -NHCO-, -SO_2N
Indicates H-, -NHSO_2-, -SO_2- or -O- group. ) General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^4^1, R^4^2, R^4^3, R^4
^4 is a substituted or unsubstituted alkyl group or R^4^
1 and R^4^2, R^4^3 and R^4^4 may be connected to form a ring, and the ring contains -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^4^5 represents an acyl group). A^4 represents an optionally substituted alkylene group. X^4 and Y^4 represent an amino group or an alkyl-substituted amino group. Z^4 represents a monovalent anion. ) General formula [V
] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X^5^■ represents an anion. R^5^1 is -Y^5-R^5^3, -Y^5-COO
R^5^3, -Y^5-OCOR^5^3, -Z^5-
COO-Y^5-OCOR^5^3, -Z^5-OCO
-Y^5-COOR^5^3, -Z^5-COO-Y^
Represents 5-COOR^5^3. [Here, Y^5 represents an alkylene group, an arylene group, an aralkylene group, and R^5^3 represents an alkyl group, an aryl group, an aralkyl group, or ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲a mathematical formula, a chemical formula,
There are tables etc. ▼ Represents. Note that R^5^4 represents an alkyl group, an aryl group, or an aralkyl group. Z^5 represents a single bond, an alkylene group, an arylene group, or an aralkylene group. ] R^5^2 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an oxycarbonyl group, an acyloxy group, an alkoxy group, an amino group, a substituted amino group, an acylamido group, a sulfamide group, a carbamoyl group, ▲Math. , chemical formula, table, etc. ▼ or represents R^5^1. However, R^5^1 and R^5^2 have at least one ester group. ) General formula [VI] A-[-(Y^6)_^6-R^6^0]_m^6 (wherein A^6 represents a group adsorbed to silver halide.Y^
6 represents a divalent linking group consisting of an atom or a group of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. R^6^0 represents an organic group containing at least a thioether group, an amino group, an ammonium group, an ether group, or a heterocyclic group. n^6 represents 0 or 1, and m^6 represents 1 or 2. )