JPS6173955A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To shorten a treating period and to save an amount of a consumption of silver and also to obtain an image having a high sensitivity and a contrasty by processing with a developer contg. a specific concn. of SO3'', a photographic material which comprises red, green, and blue color sensitive silver halide emulsion layers and contains a biequivalent coupler in the green color sensitive layer. CONSTITUTION:The above described treating method is a processing method which forms a color dye by coupling the coupler with an oxidant of a developing agent contg. an aromatic primary amine. In the method, one or more than one of the red, green and blue color sensitive silver halide emulsion layers are provided on a base body respectively, and the photographic material contg. the biequivalent coupler in at least one of the green sensitive layers is processed with the color developer contg. <=1.5X10<-2>/(l) SO3''. By processing with the developer contg. <=1X10<-2>mol/(l) SO3'', the color image having a high coloring concn. and contrasty and also a good sensitivity is obtd. To obtain the color image having the same picture-tone and sensitivity, the processing period can be shortened according to the above described method. The obtd. effect is remarkable, if the biequivalent coupler is used. Further the outstanding effect is obtd. by incorporating the biequivalent coupler to the green color sensitive layer as well as the red and blue color sensitive layers.

Description

DETAILED DESCRIPTION OF THE INVENTION C. Industrial Application Field The present invention relates to a processing method for developing a silver halide photographic material containing a two-equivalent coupler with a color developer having a low sulfite ion concentration.

(Prior Art) Two major trends can be seen in silver halide photographic materials in recent years. - IS IS
In addition to higher sensitivity, as typified by O/BOO films, the other is higher image quality in response to smaller film sizes. Regarding the former, various methods have been studied, such as increasing the size of silver halide grains, increasing the activation of couplers, and accelerating development.
E.

Farnell, J., B., Chanter, J., Pho.
togr.

Sci,,ri,7! (Iri 4/) reported that the sensitivity has already reached a plateau in the tL tiller, and even if the size of the L is increased, it cannot be expected that the sensitivity will increase much. Increasing the size of silver halide grains is accompanied by various damages such as deterioration of graininess. Many studies have been conducted on increasing the activation of couplers, but they do not contribute enough to sensitivity and have the disadvantage of worsening graininess. In order to accelerate development, it has been considered to add various development accelerators such as hydrazine compounds to the emulsion layer or developer solution, mainly for rainbow-black and white photosensitive materials, but all of these methods have resulted in increased grit and graininess. It is often accompanied by deterioration and is not practical.

On the other hand, recently color DPE (Developmen
t.

The reduction in time it takes to finish a product (Print, Enlarge) and deliver it to a customer is remarkable, and there is a strong desire to reduce the time it takes to print a single color.

C) Problems to be Solved by the Invention) Therefore, the first object of the present invention is to improve the sensitivity of at least the green-sensitive emulsion layer. The object of the present invention is to provide a method for processing a toned silver monohalide color photographic light-sensitive material. The third objective is to provide a processing method that can shorten processing time.

(Tth means to solve the problem) As a result of intensive research, we have found that the above problem can be solved by aromatic
In the Color 1 processing method in which a dye is formed by coupling with the oxidized form of the base drug, one or more layers of red-sensitive silver rhodanide emulsion-1 green-sensitive silver halide emulsion 1 are respectively formed on a support. - A silver halide photographic material having a blue-sensitive silver halide emulsion layer and containing a two-equivalent coupler in at least the green-sensitive silver halide emulsion layer has a sulfite ion concentration of t, zxio mol/ We have found that a solution can be achieved by processing with a color liquid of less than 100 ml.

The color 1 iron processing process that is currently commonly used is as follows:
Color 1 consists of a hawking process, a bleaching process, and a fixing process. In the color process.

Aromatic primary amines (1) The main ingredient is dissolved in an alkaline aqueous solution (3) Ordinary alkaline solutions are unstable against oxidation, and are currently being treated with sulfite ions, etc. Storage stabilizers (preservatives) are added. On the other hand, it is known that this sulfite ion is generated by the silver phenomenon and reacts with the oxidized product of the aromatic primary amine herbal medicine, thereby preventing the efficiency of forming a dye. (T, H
, James' The Theory of t
he Photographic Processes'
(Ko Edition, pages 3441A-J4C1).

However, the rate of formation is considered to be significantly slower than the rate of dye formation (see p. JJP-Jl!), and is considered to be significantly slower than the rate of dye formation in the photographic layer. These analyzes were not considered sufficient.

Therefore, the present inventors proposed a process in which the oxidized product of the aromatic primary amine active agent of photosensitive silver halide contained in the photographic layer couples with the diffusion-resistant coupler contained in the photographic layer [7] to form a dye. and sulfite ion and sub-11iEl sulfonation)
As a result, the deactivation to sulfite ion was found to be too large to be ignored with the couplers currently in common use, and that there was a significant decrease in the degree of color development and a decrease in sensitivity. In the so-called μ-equivalent coupler, this can be compensated for by replacing it with a 2-hit/lose coupler, but we found that there is no way to compensate for this in the 2-hit/lose coupler (Da-to-ryo coupler). , by T. H. James for two-way couplers.''
The Theory of the Photo
graphic Process-4'thed.

(described in Chapter 1). and,
The degree of sulfite ion a in the color phenomenon liquid is / X / 0
- If it is less than 2 mol/6, the color density will be high, the contrast will be high, and the sensitivity will increase for the same phenomenon time.If you want to achieve the same density, gradation, or sensitivity, you will need to shorten the color development time. It is possible that these effects ≠
It was found that when a 2-equivalent coupler was used, the results were more significant than when an equivalent coupler was used.

In the present invention, the co-equivalent coupler is used at least in the green-sensitive silver halide emulsion layer, but especially when co-equivalent coupler is used simultaneously in other red-sensitive and blue-sensitive silver halide emulsion layers, the sensitivity increases. improvement.

Remarkable effects can be achieved in terms of high contrast, silver saving, and shortening of processing time.

Here, among the λ-equivalent couplers, a typical row as the coupler core of the 2-equivalent yellow coupler is U.S. Pat.
No. 71.017, same, 1407, , Zio No.,
Id. 3.241, 104, Id. x, xyr.

4A4A3, same 3.0μ! , lWe issue, same 3. μμ7
．． 5PPI3 etc. Among these yellow couplers, acylacetamide derivatives such as benzoylacetanilide and piparoylacetanilide are preferred.

Therefore, as the yellow coupler residue (cp), those represented by the following general formulas [I] and (If) are preferable.

Note that the ax represents the bonding position of the leaving group (described later) of the co-equivalent yellow coupler.

Here, R represents a diffusion-resistant group having a total carbon number of 1 to 32 when there is no diffusion-resistant group attached to the leaving group, and when a diffusion-resistant group is attached to the leaving group (British Patent, 2, OrJ
, AμO, etc.) represents a hydrogen atom, l or m represents a halogen atom, a lower alkyl group, a lower alkoxy group, or t represents a diffusion-resistant group having a total carbon number of t to 32. R2 represents a hydrogen atom, l or t represents a halogen atom, a lower alkyl group, or a lower alkoxy group, and R2 represents a diffusion-resistant group having a total number of carbon atoms of 1 to 3. When there are λ or more R2s, they may be the same or different.

For example, nine leaving groups for the λ-sensitive yellow coupler are:
Tokko Sho≠tar/21,40, same-l coro 61, same u9-
/JJ71s% same it/-10713, same 1l-2j7
JJ%114-jllA97, JP-A-Sho μ7-co613
3, same ur-6trJ4C1 same 14r-ttr, iz,
Same 'Al-731447% Same Kota 10734, same≠2
-/Kokota, same! 0-jJ4cl, 1O-JtAuJ
2, 10-//74c23゜J/-102434.
same to-irr3-ta, same j/-/71AJr, same j/
-JtJ/, same! l-24032, same j/-10734
1. Same j/-! 31λ! , xi-rri 7301, j
'! -, 2rJII, same j4-j1922, same 12-9
0132, same 13-/314 coj1 same! → rzui,
Same j! -/2//Cobu, same j4cm Tata IAJJ, same j
44-/JJ2ri, Re5earch Disclo
sure/1013/, US Patent J, Ir? ! A, Ir.
It is described in No. 7j, No. 7j, PJJ, No. 10/, etc. Among them (active point of coupler +0-acyl substitution, -hydantoin substitution, -urazole substitution, -monoxoimide substitution).

Those substituted with -pyridanone compounds and those substituted with -sulfonyl compounds are preferred.

A representative series of coupler cores for coequivalent magenta couplers is U.S. Pat. No. 400,711.

Same, JtW, 'AI No. 2, same u, J4AJ,
No. 70J, 2. J//, No. 012, J, /J-2,
3. ! lli, lA22, same 3,0 otsuko.

No. 413, λ, No. 9101.173, 3.733
．． No. 331, British Patent No. 1, 33≠, sir. Among these Mai/Takabura, pyrazolones or pyrazoloazoles (pyrazolopyrazole,
pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, etc.) are preferred.

Therefore, the magenta coupler residue (Cp) is 1
Those represented by the following general formulas CI [), [■] and (V 2 ) are preferred.

'・-Z'' Here, R□ represents a diffusion-resistant group with a total number of carbon atoms of r to 3 in the case where the leaving group does not have a diffusion-resistant group attached, and a diffusion-resistant group is attached to the leaving group. Case (British Patent 2,01!, t
The couplers described in No. 1AO, etc.) represent a hydrogen atom, a hydrogen atom on /i or soflJ, a lower alkyl group, a lower alkoxy group, or a diffusion-resistant group having a total number of carbon atoms of r to 3-2. R2 represents a hydrogen atom, l or t represents a halogen atom, a lower alkyl group, a lower alkoxy group, or t represents a diffusion-resistant group having a total carbon number of ♂ to 32. If there are λ or more R2, they may be the same or different.

Note that the tatami represents the leaving group of the magenta coupler (described later, the bonding position).

The leaving group for the λ-equivalent magenta coupler is nine, for example:
Special Public Show≠2-3711≠, 7O-37jIAO% xi
-10ioo, same! 2-JIA ri 37, Okobi Tokukai Shomu
Turcota 431% tty-/29j3♂, 10-/
30IA1. Same 10-/22 ri 31, same jO-/J-ta 33bu, same j/-juJJ, same j/-3233, same j/
-/7μ37, same j/-/4P2F, same! /-2012
4, same j-/-Jtri Jr, same j/-10rlru2,
Same j/-//234c1% Same j/-1/2 JIAJ, same r, z -jr 22, same j3-/431291% same jμm33032, same j4cm1trjJ, same tg-
to'yaa, same jlA-1j7λ≠, same j! -1,2
1Aju, same! ! -rJOIAμ, same! j-//103
μ, same jA-310441. Same J'J-310444c
,same! Otsu-Hiroor J j, same 1t-/, 2trJJ
, same r 7-440pg, same 17-351j1. same! 7
-PAJJIA.

It is described in 17-4tJJj, 17-4tJJj, j7-26337, etc. Among these, those substituted with nitrogen-containing heterocycles (e.g., azole such as pyrazole, imidazole, triazole, etc.) - A book on substitution of alkylthio compounds -
Aryl compounds with thio substitution, aryloxy compounds with aryloxy compounds, aryloxy compounds with substitutions, etc.
The coupler core of the A0 2-equivalent cyan coupler is preferably a compound complexed with a raldehyde group or a chlorkyl aldehyde group and substituted with a cultural compound, as described in U.S. Pat. No. 772/42, for example.

ryr, txt issue, 3,002. , No. 136, 3.
03≠, rri No. 2, same 2. ≠74t, Ko 23, Same Ko,
1A23,730, same e' j 47, j J
/ No., and the same J, Q≠l, Ko3 are written in the No. etc. Among these cyan couplers, phenol or naphthol are preferred.

Therefore, as cyan coupler residues (Cpl), those represented by the linear general formulas [■], [■], [■] and NXI are preferred.

The square mark represents the bonding position of the leaving group of the 1-equivalent cyan coupler.

Here, R1 represents a diffusion-resistant group having a total number of carbon atoms of r to 3, unless the leaving group has a diffusion-resistant group, and when the leaving group has a diffusion-resistant group (British Patent Co., Ltd., 013,
≦Coupler described in 4cO, etc.) is hydrogen atom %, l or 9 is more I/rogen atom, lower alkyl group, lower alkoxy group represents a diffusion-resistant group having a total number of carbon atoms of r to 3. . R2 is a hydrogen atom! Or more no-rogen atoms, lower alkyl groups, lower alkoxy groups, or total number of carbon atoms! When there are λ or more R2's representing the diffusion-resistant group of -32, they may be the same or different.

- As the leaving group of the hypersensitive cyan coupler, for example, Akihiro Tsugami IF-/7731, IF-/7731, j-7-μr5FA,')
[ij Kaisho≠7−λ//391. Same≠7-37 Same 7-
37 Hiro-j1 same to, same! 0-ko r22t.

Same 10-ta 1323, same jO-1/7 Hiroλλ, same 10-
/JOJj4A, same evening 0- / ,? OII null, same j/-/74137. Same rt-2tr2r, same, lt/
-21121, 5r-torrui, 21-t 1
0321.1rsJj/-/4Atr2r, sameyo λ-/
1316. Mukoj Coco 0023. same! Ko! ! ! λri, same! Cota Ori 32, same! 3-3 r = 2, same rJ-
JW7tA,! , same jJ-1tJj211-1 same j3-
Hiro 7r core, same jj-1 one 31 same evening 3-tOr2λ6
, Same 3 Hiro-t≠73 Otsu, Same! μmtArλ37,! ≠−
At/CoP, same! -3λ0711 From -6! 7
,same! 6-t 3t, same j6-A2J Buddha, l'l j
& -72A IA J, same j4-27ra7. Same thing.
-61917, 64-1r00u4L, 1irlj
A-/J41J2. Same r7-JOOOJ, US Patent J, 74L? , 73! , same J, 737, 3/r, same 3
, r3ri, olAtt, 4≠, 221, 233, etc. Among these, those substituted with arylalkoxy, those substituted with alkylalkoxy, those substituted with carbonylmethoxy, those with halogen atoms CF%, Br%I
], those substituted with a sulfonyloxy compound, those substituted with a sulfonamide compound, etc. are preferred.

Specific examples of two-equivalent couplers used in the present invention are listed below, but the invention is not limited thereto.

2 equivalent yellow coupler 0OH Y-Hiroshi Y-r Y-ta y-i.

'l'-／　　ko y-/J y-iy Y-co 0 Y-2/ to 12k”25 'l'-22 " ) Q 2-equivalent magenta coupler M-/ −j α M-μ α -t α M-’y OCH3 M-i.

-14c of M-/1 M-74 x:y=Hiro yo two! ! M-/7 x:y=jo:j.

M-/ Ta M-λO M-λl H3 M-2 HiroLI (3 M-2r M-λ t l-27 z:y=!0:10 (weight ratio, same below) M-J O x:y =≠0:l, O M -J / /2 C-/J OCR2CH2SC)zU)i3 C-/ ≠ C-/j C-/A c-77CH3 C-/f C-/ri・C-20 C-co1 C-23 C-J/ OOH 15) (31(t+) The coating amount of the co-equivalent coupler used in the present invention is preferably j×IOS−co×10−3 mol/m when the cyan coupler 17t is a yellow coupler.
Preferably 1xlO to koxlO mol/rrL2
, particularly preferably λ×lo 4 ~koX10 mol/77! In the case of a L agenta coupler, it is preferably λX10 to 1XIO-E:A//m, preferably txt0 to 1xlO mol/m, particularly preferably 1xlOS-7xlO mol/rIL.

In the present invention, the ratio (mole ratio) of 9/coupler is from 1 to ioo, preferably from 3 to ! in the blue-sensitive emulsion layer. 0%, in the green-sensitive emulsion layer 1L to 300% preferably 6 to 0%
O, red-sensitive emulsion - t~j00. Preferably 1
It is 0-300.

First, if the photosensitive layer is -rf1 or more, the λ-enemy coupler should be used in the layer with higher sensitivity (for example, in the case of 3 layers consisting of a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer). is preferably a high-sensitivity layer (1 ft is a high-sensitivity layer and a medium-sensitivity layer).

In the present invention, K for introducing Kab2- into the silver halide emulsion layer is carried out by a known method, such as US Pat.

The method described in No. 3 λ, 0 λ 7, etc. is used.

For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphate esters C diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), Benzoic acid esters (e.g. octyl benzoate).

Alkylamide (gAJEha diethyl laurylamide)
, fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid ester/L
/ such as tributyl trimesate, or organic solvents with a boiling point of 30°C to 110°C 1, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, It is dissolved in β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, special public Sho Pi-syrz J, special public Sho RI-J Tata 4
It is also possible to use the polymer dispersion method described in No. cJ.

When the coupler has an acid group such as carboxyl powder or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

In the processing method of the present invention, the concentration of sulfite ions in the color developer is /, jX/ Omol/l or less,
If the concentration is higher than this, the effect of the present invention will be weakened. The sulfite ion concentration is preferably 1-oxlo mol
/ly, particularly preferably 7X/o mol/
l or less.

The sulfite ion may be used in the form of, for example, an alkali metal sulfite, an alkali metal bisulfite, or an ammonium salt thereof.

Color current IJ! In order to keep the concentration of sulfite ions in the solution low and to keep the sulfite solution stable, K has a method of replenishing the sulfite mother liquor multiple times, and a method that allows the sulfite solution to be made into air in a near-sealed state. There are methods such as keeping the sulfite ion concentration low and adding a compound to the developer that forms a stable sulfite ion adduct in an equilibrium state, but there are methods that do not allow the developer to be exposed as much as possible. Low sulfur ion concentrations may be maintained.

Compounds that form stable sulfite ion adducts with sulfite ions include, for example, compounds with aldehyde groups,
Examples include compounds containing a cyclic hemiacetal, compounds having an α-dicarbonyl group, and compounds having a nitrile group.

Specific examples of these compounds include, but are not limited to, the following compounds.

Compound sequence ■ ■ ■ ■ ■ ■ ■ OHC-(CH2)3-CHO These compounds have lo-3 to 1 per liter of color solution.
It can be used in amounts of preferably 10.10 molar gold.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin. can.

In the present invention, the gelatin may be either lime-treated or acid-treated. The details of the method for producing gelatin are described in Arthur Guais, The Macromolecular Chemistry of Gelatin, published by Academic Press, 1960.

Examples of the hydrophilic colloids that can be used include gelatin derivatives, graft polymers of gelatin and other polymers, protein derivatives such as albumin and casein; hydroxyethyl cellulose.

Cellulose derivatives such as carboxymethyl cellulose and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyhinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, and polyacrylamide. The photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver bromide, silver bromide, as silver halide, etc. Any of silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride can be used. The preferred silver halide is l! It is silver iodobromide containing less than mol% of silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 72 mol % silver iodide.

The average grain size of silver halide grains in a photographic emulsion (spherical It is the grain diameter in the case of grains approximating a sphere, and grain size is the ridge length in the case of cubic grains, and is expressed as an average value based on the projected area. 6) is not particularly limited, but is preferably 3μ or less.

The particle size can be either narrow or wide.

The silver halide grains in the photographic emulsion may have regular crystal structures such as cubic or hexagonal;
Items with irregular crystal bodies such as plate shapes, or composite forms of these crystal forms can also be used. It may also consist of a mixture of particles of various crystalline forms.

An emulsion may be used in which ultratabular silver halide grains having a diameter of 9 grains or more than j times their thickness occupy at least toX of the total projected area.

The silver halide grains may have different phases inside and outside. It may be a particle in which the fc latent is mainly formed on the surface, or it may be a particle in which the fc latent is mainly formed inside the particle.

The photographic emulsion used in the present invention is P, G1afkides.
Written by Chimie et PhysiquePh
otographjque(PauJ MonteJ
Published by the company.

/ri 47 years 1. Written by G. F. Duffin Photog
rapic Emulsion Chemistry
y (published by The Focal Press, 1996), V. L., Zelikman et al. Ma
King and Coating Photogra
phic Emulsion (The Focal
It can be adjusted using the method described in J. Press, 1996).

That is, any of the acidic method, neutral method, ammonia method, etc. can be used, and the method for reacting the soluble silver salt and soluble halogen salt can be one-sided mixing method, simultaneous mixing@, or a combination thereof. It is also possible to use a method in which zero particles are formed in excess of silver ions (so-called back mixing method).

As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is collected can be kept constant, that is, a way controlled double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Even if silver halide emulsions of fcλ or higher types are formed separately and used in combination, the same result can be obtained.

In the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt.

Iridium salt or its complex salt, rhodium salt or its complex salt,
It can also be used in the coexistence of iron salts or iron complex salts.

The soluble salts are usually removed from the emulsion after precipitation or physical ripening.As a method for this, the long-known tardel water washing method, which involves gelatinization of gelatin, may be used. Inorganic salts consisting of anions, such as sodium sulfate.

A precipitation method using anionic surfactants, anionic polymers (such as H polystyrene sulfonic acid), or H gelatin derivatives (such as fatty acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) (Floculation) can also be used.

Silver halide emulsions are usually chemically sensitized.

For the definition of chemical sensitization, for example, H, Fr1eser ed.
ie Grundlagender Photogr
aphischenProzesse mit Si
lber-halogeniden” (Akademi
scheVerlagsgesellschaft.

The method described in 4F) pages 471-73μ can be used.

That is, sulfur-containing compounds that can react with active gelatin and silver (e.g., osulfates, thioureas).

Sulfur sensitization method using reducing substances (mercapto compounds, rhodanines); Reduction sensitization method using reducing substances (mercapto compounds, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); Noble metal compounds ( For example, a noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as Pt, Ir, and Pd in addition to total complex salts can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazole, mercaptothiazole, mercaptobenzothiazoles, mercaptobe/zimidazole, mercaptothiazole Amidotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole fA (7-phenyl-mercaptotetrazole), etc.; mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines: 9 For example, oxadrine Thione thioketo compounds; azaindenes, 7'c such as triazaindenes, tetraazaindenes (especially μm hydroxy'/a-substituted (/, J, Ja, 7) tetraazaindenes), hantaazaindenes Many compounds can be added to the formulation, such as sophisticated antifoggants such as benzenethiosulfonic acid, benzenesulfinic acid, and benzenesulfonic acid amide, which are known as stabilizers.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example,
Surfactants may also be included for various purposes such as enhancement of contrast, enhancement of contrast, and sensitization.

fHJ j Hasabonin (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene Non-ionic materials such as glycolalkylamines or amide systems, polyethylene oxide adducts of silicones), glycidol derivatives (alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of tongs surfactants; alkyl carmates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines,
Carboxy groups, sulfo groups, phospho groups such as sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.

Anionic surfactants containing sulfuric acid ester groups, phosphoric acid ester groups, etc.; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaine fields, amine oxides; Cationic surfactants such as alkylamine salts, illuminating or aromatic μ-class ammonium salts, heterocyclic μ-class ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or bicyclic rings. Can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention has an increased WIc degree,
For the purpose of increasing contrast or accelerating development, for example, derivatives of polyalkyl oxide or -t such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, It may also contain midazole derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. , such as alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)
Acrylate, (meth)acrylamide, vinyl ester (for example, acetic acid vinyl ester), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) ) acrylate, sulfoalkyl (meth)acrylate, styrene sulfone, etc. can be used as a polymer having a combination of MLt components.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used are cyanine pigments and merocyanine pigments.

Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonal dyes. The pigments for %KN are pigments belonging to cyanine pigments, merocyanine pigments, and complex merocyanine pigments. For these pigments, any of the nuclei commonly used for cyanine pigments can be applied as the basic heterocyclic nucleus, i.e., pyrroline nucleus,
Oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and aromatic in these nuclei Nuclei in which hydrocarbon rings are fused, sokuchi, indolenine nucleus, benzindolenine nucleus.

Indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include nuclei with a ketomethylene structure such as pyrazoline-yone nucleus, thiohydantoin nucleus, corchioxazolidine nucleus, dione nucleus, thiazolidine-λ1μm dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc. of! ~ can be applied to the member heterocyclic nucleus.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes may themselves be used in combination with sensitizing dyes, which are often used for the purpose of supersensitization. The emulsion may contain a dye that does not have a sensitizing effect or a substance that does not substantially absorb visible light and exhibits monochromatic sensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat.
3, JRI No. 0, J, 631.7 Co. No. 1)
, aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,714!, 110), cadmium salts, azaindene compounds, and the like. The present invention is also applicable to multilayer, multicolor photographic materials having spectral sensitivities that differ at least in richness on a support. Multilayer natural color photographic materials usually include a red-sensitive emulsion layer and a green-sensitive emulsion layer on a support.
, and a blue-sensitive emulsion. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion t#j contains a yellow-forming coupler, but different combinations may be used in some cases. You can also do it.

In the photographic emulsion layer of the photographic light-sensitive material prepared using the present invention, in addition to the above-mentioned λ-equivalent coupler, ≠ equivalent dye-forming coupler, that is, an aromatic primary amine compound (for example, phenylene A compound that can develop color by oxidative coupling with diamine derivatives, aminophenol derivatives, etc.) may also be used. When surrounded, it becomes a magenta coupler.

! -Pyrazolo/Coupler 1. There are pyrazolotriazole couplers, pyrazoloimidazole couplers, pyrazolopyrazole couplers, pyrazolotetrazole couplers, virazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. For example, benzoylacetanilides, piparoylacetanilides) 1st grade, as a cyan coupler.

These include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible, having a hydrophobic group called a ballast group in their molecules, or are polymerized. It may also be a colored turnip 2-1 having a color correction effect or a coupler (so-called DIR coupler) that releases a development inhibitor during development.

In addition to DIR couplers, there are also colorless DIR couplers in which the product of the camping reaction is colorless and releases a development inhibitor.
It may also contain a campling compound. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor along with the development I.

The coupler of the present invention and the couplers described above can be used in combination of two or more types in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added to two or more different layers. Of course, there is no problem.

The photographic light-sensitive material 15)K of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salt C (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.).

Dioxane derivatives (2,3-dihydroxydioxane, etc.) %Active vinyl compounds (1,J,!-)lyacryloyl-hexahydro-5-)riazine, /,J-vinylsulfonyl-coglobanol, etc.), active halogen compounds Cλ9μm dichloro-t-hydroxy-5-)riazine), mucohalogens [8 (mucochloric acid, mucophenoxychloroic acid, etc.), etc.] can be used alone or in combination.

In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may be mordanted, such as by cationic polymers.

The light-sensitive material produced using the present invention may contain hydroquinone derivatives, aminephenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. as one-color antifoggants.

In the photosensitive material made using the present invention, the hydrophilic colloid layer may be enriched with an ultraviolet absorber. For example, benzyl substituted with aryl groups) IJ azolated compounds (e.g. those described in US Pat. No. 3.5!3.7 WJA), μm thiazolidone compounds (e.g.
ri Buddha name, same J, JjJ.

tri), benzophenone compounds (for example, those described in JP-A No. 4-271), cinnamate ester compounds (C series), US Patent No. 3.7 or, ROJ, same! , 707.371), butadiene compounds (such as those described in U.S. Pat.

oar, No. 222) or benzoxidol compounds (listed in US Pat. No. 3,700, France!!
) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming graphite), an ultraviolet-absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for the purpose of preventing irradiation or as a lubricant. Such dyes include oxonol dyes, hemioquinol dyes, methylyl dyes, merocyanine dyes, cyanine dyes and azo dyes, among which oxonol dyes; hemioquinol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and one or more electrolytic corrosion stabilizers used in the present invention may also be used in combination. Known anti-fading agents include /S hydroquinone derivatives, gallic #l
There are derivatives, p-alkoxyphenols, p-oxyphenol derivatives, bisphenol 9, and the like.

For photographic processing of the layer consisting of the photographic emulsion made using the present invention, any of the known methods and known processing solutions such as those described on pages 30 to 30 may be used. can also be applied. The processing temperature is usually chosen between /r'c and zooc, but
The temperature may be lower than 0c or higher than IO'c.

The first aromatic amino color developer used in the color developer in the present invention includes known ones that are widely used in various color photographic processes. These developing agents include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally present at a concentration of about 0, ig - 3017 for color developer lJl/l, more preferably about i for color developer/llIc.
g - used at a concentration of about i3 g.

Examples of aminephenol-based sludges include O-aminophenol, p-aminephenol, and more! It is enriched with -amino-cooxytoluene, rhoamin-3-oxytoluene, -mono-oxy-3-amino/, 4C-dimethyl-benzene, and the like.

A particularly useful seventh aromatic amine color developer is N.

It is an N-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted.

Among them, examples of particularly useful compounds include N,N-diethyl-p-7 22-diamine hydrochloride, N-methyl-p-7
-Fuji Nishin Diamine! acid salt, N.

N-dimethyl-p-phenyl diamine hydrochloride.

λ-Aminoj-(N-ethyl-N-dodecylamino 1
-) Luene % N-Ethyfluhe β-methanesulfonamidoethyl-3-methyl-μm aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, IA-amino-3-methyl-N,N-diethyl Aniline% ≠-amino-N-2C2-methoxyethyl
-N-ethyl-3-methylaniline-p-toluenesulfonate.

In addition to the first aromatic amino-based color developer, the alkaline color developer used in the present invention further contains various components (1, for example, hydroxide) that are usually added to the color developer. It can also optionally contain alkaline agents such as sodium carbonate and potassium carbonate, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners. The pH value of this color development solution is usually 7 or more, most commonly about 2 to about 13.

The method of the invention can also be used for color reversal processing.

In the present invention, the black-and-white developing solution used at this time may be a so-called black-and-white first developer solution used in the reversal processing of color photographic light-sensitive materials, which is commonly known, or a developer used in the processing of black-and-white light-sensitive materials. ti may contain various well-known additives commonly added to black and white developers.

Typical additives include developing agents such as l-phenyl-3-pyrazolidone, metol and nohydroquinone, preservatives such as sulfites, and alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. Preservatives, potassium bromide, inorganic or M-loss inhibitors such as λ-methylbenzimidazole and methylbenzthiazole, water softeners such as poly-IJ and IJ-phosphates, trace amounts of iodides, Mention may be made of development inhibitors consisting of mercapto compounds.

In the bleaching solution or bleach-fixing solution constituting the present invention, a bleaching agent with a weak bleaching blade is used. One example is a ferrous ion complex, which is a complex of ferrous ion and a chelating agent such as an aminopolycarbo/acid or a salt thereof. Aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are salts of aminopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amines. Examples of alkali metals include sodium, potassium, lithium, etc., and water-based amines include alkyl amines such as methylamine, diethylamine, triethylamine, and butylamine, 8-ring amines such as cyclohexylamine, aniline, m-
) chiarylamines such as luidine, and heterocyclic amines such as pyridine, morpholine, and piperidine.

Typical examples of chelating agents such as these aminopolycarboxylic acids and aminopolyphosphonic acids or their salts include: ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid disodium salt ethylenediaminetetraacetic acid diammonium salt ethylenediaminetetraacetic acid tetra(trimethylammonium) salt ethylenediamine Tetraacetic acid tetrapotassium salt Ethylenediaminetetraacetic acid tetrasodium salt Ethylenediaminetetraacetic acid trisodium salt Diethylenetriamine is ntaacetic acid, intasodium salt Ethylenediamine-N-(β-oxyethyl)-N,N
', N'-) to ethylenediamine acetate-N-(β-oxyethyl)-, N
', N'-1 trisodium acetate ethylenediamine-N-(β-oxyethyl)-N, N', N'
-triammonium salt of triacetate propylene diamine tetraacetic acid propylene diamine tetraacetic acid disodium salt nitrilotriacetic acid nitrilotriacetic acid trisodium salt cyclohexanediamine tetraacetic acid cyclohexanediamine tetraacetic acid disodium salt iminodiacetic acid dihydroxyethylglycine ethyl ether diamine tetraacetic acid glycol ether diamine tetra Ethylene diamine acetate tetrapropionate phenylene diamine tetra acetate/, J-diaminobronobutyl alcohol-I N I N'
IN/-tetramethylenephosphonic acid ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid i,3-propylenediamine-N,N,N'.

Examples include N/-tetramethylenephosphonic acid, but the compound is not limited to these exemplified compounds.

fi/c iron io/complex salts may be used in the form of complex salts, and ferrous salts 1 such as ferrous sulfate, ferrous chloride, nitric acid@λ
A ferrous ion complex may be formed in a solution using iron, ferric ammonium sulfate, ferrous phosphate, etc., and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc. . When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferrous salt and a chelating agent, one or more types of ferrous salts may be used. Furthermore, one or more types of chelating agents may be used. Also.

In either case, the chelating agent may be used in excess of the amount required to form the ferrous ion complex.

Also, a bleaching solution or bleaching constant containing the above ferrous ion complex
The II liquid may contain metal ion complex salts other than iron, such as cobalt and copper, or hydrogen peroxide.

The persulfate used in the bleach solution or bleach-fix solution constituting the present invention is an alkali metal persulfate such as potassium persulfate or sodium persulfate, or ammonium persulfate. The bleaching accelerator of the present invention is of course effective against persulfuric acid salts, but exhibits a particularly remarkable effect on ferric ion complex salts.

In addition to bleaching agents such as ferric ion complex salts and the above compounds, the bleaching solution constituting the present invention includes bromides such as potassium bromide, sodium bromide, ammonium bromide, or chlorides such as potassium chloride, sodium chloride, A regenerating agent such as ammonium chloride may be included. In addition, 1 or more species with a pH buffering capacity of M such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Inorganic acid.

Additives commonly known for use in bleaching solutions, such as organic acids and their salts, can be added.

In this case, the amount of bleach per 1 liter of bleaching solution is 0°/, 2 mol, and the pH of the bleaching solution during use is %3.0-1.0 in the case of ferric ion complexes, especially μ, θ~7.77
It is desirable to become

On the other hand, when the composition of the present invention is used as a bleach-fixing agent, conventional fixing agents, i.e. thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate: sodium thiocyanate, thiocyanic acid Thiothia/acid salts such as ammonium and potassium thiocyanate: ethylene bisthioglycolic acid % 3. Water-soluble silver halide solubilizers such as thioether compounds such as 6-cythyl, l-octanediol and thioureas; These 4/species can be used in combination of λ or more types.
A special bleach-fixing solution consisting of a combination of a fixing agent of -/jtjJj4A and a large amount of a halogen compound such as potassium iodide can also be used.

The value of each component in the bleach-fix composition is 1! ! 4 White fixer/l % The ferric ion complex salt is desirably 00 l-comole and the fixing agent is O, 2 to 4 moles.

Bleach-fixing agents include the above-mentioned additives that can be added to the bleach solution and rA salts as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite of hydroxylamide, hydrazine, and aldehyde compounds. wcCIi salt adducts, acetaldehyde sodium bisulfite, etc. can be enriched if fed. Furthermore, various fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as methanol can be used.

Bleach solutions, bleach-fix solutions, and their prebaths contain compounds already known as bleach accelerators, such as U.S. Pat. No. 31,131.
Specification No. 11, German Patent No. 1 J 0112 specification,
The same Jozyyrr issue details, Tokukai Sho! 3-3 Core No. 77, No. 13-171J1, J'yuir, JJ-jj73, J3-7Co6, No. J-ta! ≦30. Same j3-2! 637th newsletter, same 13-1044 Ko JJ bulletin, same jJ-/, 14!
Publication No. 4, JJ-/Publication No. 74 J, No. 11-
-! μ No. z Publication, Research Disclosure No. 17
Mercapto group or disulfide group described in /λ number t
- Compounds with thiazolidine derivatives such as those described in JP-A-10-/μ0/CO-2, JP-A-1989-/μJ-1
No. 104, Japanese Unexamined Patent Publication No. 12-20132, JJ
-32731, U.S. Patent No. 3701. Thiourea derivatives described in specification z6/, German Patent No. 1/Core 7
1! No. specification, v# Iodide described in Kaisho 17-142Jj, German Patent No. 966μ10, No. 27
141≠30, polyamine compounds described in Japanese Patent Publication No. 141≠No. 3-2 μm Publication No. 27, same μm
317 Co. No. 7, No. 11-24101. No. Publication, same!
r-/4Jfg□ publication etc. can also be used together.

In addition, the pH of the bleach-fix solution is usually μ, o
,y.

0, particularly preferably 7.0-r, 0.

Bleach or whitening agent compositions as described above are meant both during bleach-fixer formulations for preparing bleach solutions as working solutions or replenisher solutions. In the case of a preparation containing two or more liquids, the pH of the liquid containing the @-iron ion complex salt t-t can be further increased, regardless of the above pH range.

The processing method of the present invention comprises processing steps such as the above-mentioned color development, bleaching, and fixing. After the fixing step or bleach-fixing step, processing steps such as washing with water and stabilization are generally performed; A simple treatment method such as performing only a stabilization treatment step can also be used.

The rinsing water used in the rinsing step can contain known additives, if necessary. If kept, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid,
A bactericidal agent or antifungal agent to prevent the growth of various bacteria and algae, a hardening agent such as a magnesium salt or an aluminum salt, a surfactant to prevent drying load and unevenness, etc. can be used. Maku is L, E, West, "Wate"
rQuality Cr1teria' Photo
,Sci,andEng,,vol,RIMA pag
e J 4C4cmJ j F (tY&!1 etc. can also be used.

Further, the washing step may be carried out using a tank of λ tank or more if necessary, and the washing water may be saved by performing multi-stage countercurrent washing (for example, co-stages).

As the stabilizing solution used in the stabilization step, a processing solution that can stabilize a single-dye image is used. For example, a liquid having a buffering capacity of pH 3 to 4, a liquid rich in aldehyde (for example, formalin), etc. can be used. A fluorescent brightener, a chelating agent, a bactericide, a fungicide, a hardening agent, a surfactant, and the like can be used in the stabilizing liquid as necessary.

In addition, the stabilization process may be carried out using a tank larger than the Shiko tank if necessary, and the stabilizing liquid can be saved by performing multi-stage countercurrent stabilization (for one row, 2 to 2 stages), and furthermore, the water washing process can be omitted. You can also do it.

(Practical row) Practical row L A magenta coupler (M-J) was dissolved in tricresyl phosphate and ethyl acetate on a tri-acid cellulose support with an undercoat, and emulsified and dispersed in a gelatin bath solution. Sample A was prepared by adding an emulsion layer as shown below. The amount of each substance applied is expressed in parentheses as 9/ml or mol/m2.

(1) Emulsion layer Negative silver iodobromide emulsion (silver iodide 10 mol% grain size/, fμ silver r, jXlo' mol/m) magenta coupler M-J ty, xxio' mol/m) tricresyl 7
Male 7ate (2,0,9/m2) Gelatin (2,10g/m2) (2) Protective layer gelatin (K,j09/m2) 21μm dichloro-5-hydroxy-3-) lyazine sodium salt C'-'J9/m2) After this film was left at μo0c and 70% relative humidity /4C4C, it was exposed to white light for sensitometry, and the next color development process (a-d) I did this.

Color actual processing process 1 Color actual @ J'/In Jr0C2 drift
White Ko' / 0 1
1゜3 Water washing ko' I 4 Fixing ko' I 5 Water washing ≠' 1 6 Stable /' y Here, the composition of each processing solution in the color development process is as follows.

Colored mother liquor water 100rr
tl Hiro-(N-ethyl-N-hydroxyethyl)amino-comethylaniline/sulfur! 1 platform! ? Sodium sulfite X? Hydroxylamine sulfate potassium carbonate
JOf Potassium Bicarbonate 1.
Ko? Bromide power + 1 um l"21 salt 1
Add trisodium triacetate to 0.4 hysodium and add water.
/l (pH/0, t) where the amount of sodium sulfite x no l/l is a
In the processing, j, 0f(uXlo 'mol/l), b processing TeIti2, ! ? (JX/0'mol
/l), c processing tail/, 09 (0,
rX/0'mol/l) and o in the d treatment,
xry(o, koX/0-'mo)/ri.

Bleach solution water 100 ferric ammonium salt of ethylenediaminetetraacetic acid 100f ethylenediaminetetraacetic acid 10? Potassium bromide /jO? acetic acid
? add water
1lCpH&,0) Fixer water 100m
1 ammonium thiosulfate 1jOf sodium sulfite 10f sodium bisulfite 2. Jf add water
1IC pH4,0) Stable liquid water room
Formalin (37g) jmJ Drywell 3g Add water
The density of the processed sample was measured using green light to obtain photographic data, and the photographic results are shown in Table 1.

From Table 1, the sulfite ion concentration in the color current I# liquid is '
It is clear that C processing and d processing below X/Omol/l result in higher sensitivity and higher contrast.

Example 2 To evaluate the effectiveness of compounds of the present invention (cellulose)
A multilayer color photosensitive material sample 20 was prepared on a II acetate support, each layer having the composition shown below.

The amount of emulsion coated was expressed by the amount of coated trowel.

(Sample 2oi) 1st layer: Anti-ration layer black colloidal silver o, 1ry7 milk 2 ultraviolet absorber '[J - / O0/2t/fi2
Gelatin layer first layer containing U,2 0.1717 m'': intermediate layer λ,j-Gt- is tadecylhydroquinone o,iry/m2 coupler
Cp-70, / / f / @2 Gelatin layer containing iodine f complex emulsion 0.1177 m2 3rd layer: 7th red-sensitive emulsion layer Silver iodobromide emulsion o, tsy/rrL2 sensitizing dye I... 7.0 x 10-5 moles per mole of silver Sensitizing dye■...Co, 0xlO per mole of silver Sensitizing dye■...Co, rXio' mole increase per mole of silver Sensitive dye■...Co, OX/0 mole coupler cp io, oxo for 7 moles of silver? /rn2 coupler 'cp-20,0YJ'? /rrL2 coupler
cp J O,ji y/,z coupler cp
-@ Gelatin layer containing 0.010f/rrL2 μth layer: 2nd red-sensitive emulsion layer Iodorous odor [arsenal emulsion l-Otf/m2
Sensitizing dye ■...j, λxio' molar per 1 mol of sensitizing dye ■...JXlo' molar per 7 mol of silver Sensitizing color X1ff...co , /xIO'
Molar sensitizing dye ■.../, jX/ 0-5 mol coupler Cp -/ 0, Oj/f per 1 mol of silver
/ TrL ”Coupler C,-co 0.io
t/m2 coupler Cp-J O, OA/
y/rIL2 coupler Cp -p 0.0
(7j f/rrL2 coupler Cp-j
O, 0≠47/. 2 gelatin layer 1st layer: 3rd red-sensitive emulsion layer JJ) J! Emulsion / , A f / m 2 Sensitizing dye I... J, j x 10' mol per mol of silver Sensitizing dye ■... -/ , 4X/ per mol of silver
0 molar sensitizing dye ■...Co, JX10 per mole of silver Sensitizing dye ■...i, i, Xio per mole of silver S molar coupler Cp-J 00OjO? 6th layer: Intermediate gelatin layer 7th layer: 1st green-sensitive emulsion layer Iodobromide steel emulsion 0. rjfl door 2 sensitizing dye■...J for 7 moles of silver, 1rX10 'mol sensitizing dye■...J for 1 mole of silver, 0x10''-r::ru sensitizing dye■... For 1 mole of silver/, 2 x 10' mole coupler cp-40, 2ta f/m" coupler Cp-70, 0 hof/m2 coupler Cp-1r
O, Oj! ? /Employed 2 Coupler Cp-ta
o, oj≠? /m2 layer: 2nd green-sensitive emulsion layer: Arsenic emulsion i, zy7□2 sensitizing dye ■... j, 7X/(7'-l sensitizing dye ■ ... co, /XIO' mol per mole of silver sensitizing dye■...t,!x10 5 mole coupler c, -aO, cojt/rr L2 coupler C
p -70,0/ J t / z 2 force i5- C
p-IO,002t/m” coupler C
p-20,010? / Gelatin layer containing 2: 9th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion 1. zt/m2 sensitizing dye■...for 1 mole of silver! , 0xlO molar sensitizing dye ■... # 4 cxlO molar sensitizing dye ■... Hal XlO molar coupler for 7 mol of silver Cp-100,070f/1rL" coupler Cp-70 , 0/ J f/m 2 tricresyl phosphate O0μ0 ?/gelatin layer containing milk 2 1st O layer: yellow filter more yellow colloidal silver o, otAt/m”2, r
-Gelatin layer containing t-t-interdecylhydroquinone o,oJlf/m" Eleventh layer: 1'fr emulsion layer "Silver iodobromide emulsion 0.32f/m2 coupler cp-//o,yyt/m2 coupler C
p-/2 0.02r? /7FL2 tricresyl phosphate), 0.1 cot/m2 gelatin layer 1st co-layer: blue-sensitive emulsion layer odour (arsenic emulsion 0-4'Of/m'' coupler)
Cp - / / 0, coj S'/m" tricresyl phosphate) 0./7 t/m2 sensitizing dye ■... Gelatin containing 10' mol of ko, ko for 7 mol of silver Layer 73: Fine grain emulsion layer Gelatin layer containing silver iodobromide emulsion O,!j?/m" Seventh layer: j1r-sensitive emulsion layer Silver iodobromide emulsion /, 00? /mZ coupler Cp-//0, Jco f/m
"tricresyl phosphene) 0.lu ?/m2 sensitizing dye ■... Co per 1 mole of silver, JX/(7' mole It layer: 1st protective layer ultraviolet absorber U-to, la P/+rt2
Gelatin layer containing ultraviolet absorber U-20,-co f/m2 16th layer: First protective layer polymethyl methacrylate particles (diameter/, jμl O,0!?/m2 Fluorine compound p-/ In addition to the above composition, gelatin hardener H-7 and a surfactant were coated on each layer of the gelatin layer containing 0.00 u?/m2 silver emulsion 0.3 O9/m2.

This sample was subjected to uniform sensitometric exposure and developed under the following three conditions: 1st-order color developer processor and B's color development time: did. The density of the developed sample was measured using true color light. The photographic properties obtained are shown in Table 2.

Color development (to) processing 1 Bleach fixing Jt oc Water washing Jrc
IC 7 minutes 75 seconds stable Jr'CJ minutes is seconds Dry processing liquid composition (color current solution) Sodium nitrilotriacetate / , Of sodium sulfite J, 0f (A treatment) 1.0f (B treatment) Sodium carbonate Jo, Of odor 1 Hikari 1. ≠? Hydroxylamine sulfate λ, 4L? Hiro-(N-ethyl-N
−β− Hydroxyethylamino) monomethylaniline sulfate μ,! add water
/lj (bleach-fix solution) Ethylenediaminetetraacetic acid, ferric ammonium salt, -2 water [100, Of ethylenediaminetetraacetic acid disodium salt!・Of ammonium thiosulfate aqueous solution (70 tttl) Sodium sulfite io, oy Add water /, 01 pl (A, j (stable g) Formalin t Go Add water /1 From Table 2, the present invention It can be seen that it is possible to obtain photographic performance equivalent to processing with a high sulfite ion concentration by applying the next color photographic processing in one hour.

cp-j [t)C5H1l Cp-≠ Cp-r Cp-A CI)-7 a C,-r p-2 (p-/ 0 6 (p-//Cp-/J ■ =178o2N)T( CFz)sOcH2cH2N(C
H313 Sensitizing Dye I 2H5 C2) T5 ■ 2H5 Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment July 2, 1972 1, Case Indication Showa! First special request of 2019, 73 pieces!
No. 3. Relationship with the case of the person making the amendment Patent applicant's office 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment Column 5 of "Detailed description of the invention" in the specification, "Invention" in the description of the contents of the amendment All entries in the "Detailed Explanation" section have been amended as follows.

(1) No. 1! λth line from the bottom of the page "l×10-2" "/,!×70" and correct it.

(2) In the second line of the first page, after "-pyridanone compound substituted", insert "-azole substituted (for example, pyrazole, imidazole, triazole substituted)".

(3) "-Aryl compound thio substituted" on page 2/line j is corrected to "-aryl thio compound 6-substituted."

(4) Part of structural formula M-22 on page ≠Q “ and correct it.

(5) No.! λ page 6-7 lines "Agenta coupler" "Magenta coupler" and correct it.

(7) Page t6 Hiroki "Making rpH history" Raise the rpH even higher.” and correct it.

(8) Page 70 // line [Xmot/lJf.

rxP(mot/lj and correct it.

Claims (1)

[Claims] In a color development process in which a dye is formed by coupling with an oxidized product of an aromatic primary amino developing agent, one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more green-sensitive silver halide emulsion layers are provided on a support. A silver halide photographic light-sensitive material having a blue-sensitive silver halide emulsion layer and containing a two-equivalent coupler in at least the green-sensitive silver halide emulsion layer has a sulfite ion concentration of 1.5 x 10^-^2 mol.
A processing method characterized by processing with a color developer of /l or less.