JPH021846A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent generation of contamination of picture images and generation of fog due to deposition of dissolved pigment or dye even in a low replenishing processing by processing an internal latent image type sensitive material with a color developing soln. contg. a specified compd. CONSTITUTION:A sensitive material constituted of >= one emulsion layer contg. internal latent image type silver halide particles, is developed with a color developing soln. contg. a compd. expressed by the formula I, wherein the development is performed while replenishing 0.1-2.5 mililiter developing soln. per 100m<2> sensitive material. In the formula, each R1 and R2 is H or a 1-5C alkyl which may have a substituent. A compd. expressed by the formula II may be usable as a hydroxylamine deriv. expressed by the formula I. Deposition of a dye, etc., dissolved out of the sensitive material to the sensitive material to be processed is prevented by this method even if the processing is performed under low replenishment condition, and the fluctuation of the minimum density and decrease of the maximum density during a running processing are both prevented.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a silver halide color photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material) which prevents the occurrence of fog in unexposed areas and has excellent processing stability. Regarding the processing method of .), in detail, it is necessary to prevent stains and fog caused by the adhesion of pigments or dyes eluted from the light-sensitive material to the processed light-sensitive material, and to prevent fluctuations in minimum density (Dmin) during running processing. The present invention also relates to a method for processing a photosensitive material that maintains the stability of a one-color developer and also prevents a decrease in maximum density (Dn+ax).

[Background of the Invention] Methods used to create images using conventionally known direct positive photosensitive materials can be divided into two main types.

One type uses a silver halide emulsion that has been fogged in advance, and uses solarization or the Burschel effect to destroy the fogging nuclei (latent image) in the exposed area to create a positive image after development. be.

The other type uses an internal latent image type silver halide emulsion that has not been fogged in advance, and after image exposure, fogging treatment is performed or surface development is performed while fogging treatment is performed to obtain a positive image. .

Here, the fogging treatment may be performed by exposing the entire surface to light, chemically using a fogging agent, using a strong developer, heat treatment, etc. Methods using light or fogging agents have been adopted. The term "internal latent image type silver halide emulsion" refers to a silver halide emulsion which has photosensitive nuclei mainly inside silver halide grains and forms a latent image inside the grains upon exposure.

This latter type of method is more sensitive than the former type - for boat fishing, and is suitable for applications requiring high sensitivity, and the present invention is particularly concerned with this latter type. .

Various techniques are known in the art. For example, U.S. Patent No. 2,592,250;
No. 466.957, No. 2,497,875, No. 2,5
No. 88,982, No. 3,761.261i, times: l,
No. 761,276, same: l, 796.577 Su and Kuni Toku 1 work 1.15! , 36: The main thing C is listed in No. 1 Kasa.

By using these known methods, it is possible to produce directly positive-type photosensitive materials with relatively high sensitivity.

Regarding the formation mechanism of positive images, for example, the Photographic Science and Engineering Link (Ph.D.
otographic 5science and en
gineer-iB) Volume 20, Page 158 (+976)
As stated in , it is considered as follows. That is, photoelectrons generated within silver halide crystal grains by imagewise exposure are selectively captured inside the grains, forming internal latent images. This internal latent image acts as an effective trapping center for electrons in the conductive band, so in exposed particles, electrons injected during the subsequent fog development process are captured internally and strengthen the latent image. It turns out. In this case, the latent image is all internal and is not developed. - For particles that have not undergone imagewise exposure, at least some of the injected 'electrons are captured on the particle surface and the particle is developed by surface development.

Is it possible to produce photosensitive materials that form positive images by using the above-mentioned known techniques? In order to apply these photosensitive materials to various photographic fields, further improvement in photographic performance is desired. .

Particularly, in recent years, there has been a tendency to reduce the amount of replenishment of color developing solutions from the viewpoint of preventing pollution and preventing pollution of the social environment. At this time, pigments and dyes eluted from the photosensitive material accumulate in the color developer and adhere to the photosensitive material, causing stains on unexposed areas.
It has been found that this coloration plays the role of a filter during flash exposure of internal latent image type photosensitive materials and has a great influence on photographic properties. These effects and drawbacks have become more and more significant due to the recent emphasis on reducing the amount of replenishment, and have become a problem that cannot be ignored. Furthermore, due to this low replenishment, the residence time of the color developer in the automatic processor becomes longer, which increases the probability that the color developer will be oxidized and decomposed, and the coloring due to the oxide of the base agent is also caused by internal latent image type photosensitive This is becoming a very serious problem for materials.

Various antioxidants (preservatives) can help solve these problems.
After studying the above, we found that the above problems could be solved only by using a specific hydroxylamine derivative, which can improve the above drawbacks of the conventionally used sulfites and water-soluble salts of hydroxylamine. I found out.

In particular, the minimum density (D
It was found that the effect of suppressing fluctuations in +ain) was remarkable, and that it was possible to prevent a decrease in maximum density (Dmax) without deteriorating stability.

[Purpose of the Invention: That is, the first object of the present invention is to use photosensitive materials for low replenishment.
Another object of the present invention is to provide a method for processing a photosensitive material in which stains and fog caused by adhesion of pigments and dyes eluted from the dye to the photosensitive material to be processed are improved, and stable photographic properties are provided over a long period of time. The second objective is to provide a method for processing photosensitive materials that prevents fluctuations in the minimum density (Dmin) during running processing, maintains the stability of the color developer, and prevents a decrease in the maximum density (Dmax). There is a particular thing.

[Means for Solving the Problems] The present invention achieves the above object in a method of processing a photosensitive material including one-color development treatment, in which a photographic emulsion layer containing internal latent image type silver halide grains is formed in the photosensitive material. A photosensitive material formed by coating at least one layer on a support, wherein the color developer contains a compound represented by the following general formula [A], and the amount of replenishment of the color developer is 0 per +00 crn' of the photosensitive material. .1 to 2.5111.

General formula [A] In the formula, R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. However, R1 and R2
It cannot be both a hydrogen atom and a hydrogen atom at the same time. Further, 1 (1 and 1) may form a ring (for example, may form a heterocycle such as piperidine or morphone).

The present invention will be explained in detail below.

The processing process used in the present invention is a color development process including a color development process.

In particular, it is preferable to perform a color development process, a bleaching process, a fixing process, and a water washing or water washing alternative stabilization process, but instead of the process using a bleach solution and the process using a fixing solution, The bleach-fixing process can also be carried out using bath bleaching constant I7 solution.

In addition, in combination with these treatment steps, a pre-hardening treatment step,
A neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed.

The color developer used in the present invention refers to a surface developer that does not substantially contain a silver halide solvent, and the color developing agent contained in the color developer is an aromatic primary amine-based developer. Contains color developing agents, amine phenolic and p
-Contains phenylenecyamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, such as hydrochloride, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. .

These compounds are generally about 0.0% in color developer 11.
Concentrations from 1 g to about 200 g, more preferably from about 1 g to 50 g.
Use at a concentration of g.

In addition, the processing temperature with color developer is 10°C to 65°C.
The temperature is preferably 25°C to 45°C.

Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, 5-aminophenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

Particularly useful aromatic primary amine color developers are N, N
"-Dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted (, z.

Among them, particularly useful examples include N,N'dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N-methyl-p-phenylenediamine hydrochloride.
-phenylenediamine hydrochloride, 2-amino-5-(N-
ethyl-N-dodecylamino) ~ toluene sulfate, N-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β
-Hydroxyethyl-3-methyl-4-aminoaniline sulfate, 4-amino-3-methyl-N,N = diethylaniline sulfate, 4-amino-N-(2-methoxyethyl)-N-ethyl-3 -Methylaniline-p-toluenesulfonate and the like.

Further, the above color developing agents may be used alone or in combination of two or more.

The color developing solution of the present invention contains a compound represented by the general formula [A].

First, a supplementary explanation will be given regarding the general formula [A].

In general formula [A], R1 and R2 may be the same or 11
When R+ and/or R2 represent an alkyl group, the alkyl group includes those having substituents. Examples of the substituent include a sulfonic acid group, a hydroxy group, an alkoxy group (methoxy group, a hexyl group, a propyloxy group, etc.), a carboxy group, an amino group, and the like.

Preferred exemplary compounds among the compounds represented by the general formula [A] are shown below.

(1) C) If-NH-Kano (2) C2Hs-Ntl-0) 1 (3) 1so-C: +H, -Ntl-0) 1 (4)
C3+1. -N11-011(5) +1O-e
ll□-Nil-011(5) C11:l-0-C
211,-Nil-011(7) +1O-C21+
, -Nil-011(8) 1100cmC2+1.
-Nll-OH(9) ll03S-C2H, -NH
-OH(10) N211-(:, H6-Nil-0
11 (11) Czlls-0-CJI<-Nll-O
ff(12) lo-C211,-0-C211,-N
il-011 These compounds are usually in the free form
is used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate, phthalate, phosphate, and acetate.

These include, for example, U.S. Pat. No. 3,287,125;
It can be easily synthesized by the method described in No. 293, No. 334, No. 3,287,124, etc.

The concentration of the compound represented by the general formula [A] in the color developer is usually, for example, preferably from 0.1 g/l to 50 g/l, more preferably from 0.3 g/l to 30 g/l. The amount is particularly preferably 0.5 g/l to 20 g/l.

Further, the above compounds may be used alone, or in combination of two or more.

In the present invention, it is particularly preferred to use a sulfite or a sulfite ion-releasing compound in combination with the compound represented by the general formula [A].

Specific examples of sulfites or sulfite ion-releasing compounds include potassium sulfite, sodium sulfite, ammonium sulfite, sodium metabisulfite, potassium metabisulfite,
Examples include bisulfite adducts of formaldehyde, bisulfite adducts of acetaldehyde, bisulfite adducts of propionaldehyde, and bisulfite adducts of glutaraldehyde.

The concentration of the above compound is 1 per color developer, Ox 10
-'~], OX may be in the range of 10-' mole, but if a large amount of sulfite and sulfite ion-releasing compound is present,
This tends to cause a decrease in the coloring density of the dye in the photosensitive material, so 5. Ox 10-'~5, Ox 10-2
It is a mole.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. Additionally, various additives such as alkali metal halides (potassium chloride, etc.) may be included. Further, it may contain a development regulator such as citradinic acid. Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylformamide, or dimethyl sulfoxide can be appropriately contained.

The pH of the color developing solution used in the present invention is 9 to 12,
Preferably 9.2 to 10.1, particularly preferably 9
．． It is 4-9.8.

The color developing solution used in the present invention optionally contains tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, hendose or hexose, pyrogallol 1 as an anti-thickening agent. .3-dimethyl ether or the like may be contained.

In the color developing solution used in the present invention, various chelating agents can be used in combination as metal ion-1 chaining agents. For example, as the chelating agent, amine polycarboxylic acids such as ethylenecyaminetetraacetic acid and diethylenetriaminopentaacetic acid, organic phosphonic acids such as l-hydroxyethylidene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), or ethylenecyamine Aminopolyphosphonic acids such as tetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,3-)-ricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexamethanoic acid , polyhydroxy compounds, etc.

In the color developer of the present invention, the amount of replenisher added to the color developer is 0 per photosensitive material to be processed + 00 crn''.
．． 1~2.5mJlj, preferably 0.2~2m
1, more preferably 0.4 to 1.2 rn sentences. Replenisher level for the color developer of the present invention: 0.1mM/l
If the amount is less than 00 crn', the amount of processing liquid that adheres to the photosensitive material and taken out is too large to be effectively processed, and if it exceeds 2.5 nl/100 cm', it is undesirable from a pollution standpoint. In addition, there is a drawback that fogging is more likely to occur.

Furthermore, it is preferable that the color developing solution of the present invention does not substantially contain pencil alcohol.

In the present invention, the bleaching process refers to a process of bleaching the developed silver image after the color development process with an oxidizing agent (bleaching agent).

17j As the whitening agent, a total complex salt of an organic acid is preferably used, such as a polycarboxylic acid, an aminopolycarboxylic acid, or an organic acid such as oxalic acid or citric acid, coordinated with a metal ion such as iron, cobalt, or copper. is used. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following. That is, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 3-propylenediaminetetraacetic acid, and the like.

These bleaches contain 5 to 450 g/t, more preferably 2
Use 0 to 250 g/Jl.

In addition to the bleaching agent mentioned above, it is preferable to add a halide such as ammonium bromide to the bleaching solution. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may also be used. can.

In the present invention, the fixing process refers to a process of desilvering and fixing using a fixing solution containing a silver halide fixing agent. Silver halide fixing agents used in the fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as thiosulfates, thiocyanates such as ammonium thiocyanate, thioureas, thioethers, and the like. These fixing agents should be used in an amount of 5g/l or more that can be dissolved, or generally 70g/l to 250g/l.
and use it.

In the present invention, it is preferable that the bleaching process and the fixing process are performed in one process using a bleach-fix solution,
The metal rust salt of an organic acid used in the bleach-fix solution is a metal rust salt of an organic acid such as aminopolycarphonic acid, oxalic acid, citric acid, etc., coordinated with metal ions such as iron, copper, etc. It is something. As the organic acid used to form such a metal complex salt of an organic acid, the same organic acid as the t1 white liquor can be used.

As the silver halide fixing agent contained in the bleach-fixing solution, a compound which reacts with silver halide to form a water-soluble complex salt, such as those used in ordinary fixing processes, is used.

Further, the bleach-fixing solution according to the present invention has the following general formula [I]
When containing at least species of the compound represented by ~[IX], the desired effects of the present invention are better achieved, and there is also another effect of improving precipitation caused by silver in the bleach-fix solution. Therefore, in the present invention, it is more preferably used.

General formula [I]? C=S [In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocycle (including 5- to 6-membered unsaturated rings or fused rings), and R1 is a hydrogen atom, a carbon atom Number 1 to 6 alkyl groups, cycloalkyl groups, aryl groups, Peter g1 groups (5 to 6
(including those in which 6-membered unsaturated rings are condensed), or represents an amino group. general formula [II] [wherein R7 and R1 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group,
Amino group, acyl group having 1 to 3 carbon atoms, aryl group,
Or represents an alkenyl group.

A represents or n, a valent heterocyclic residue (including those in which 5 to 6 unsaturated rings are fused), and X is =S, -〇 or =N
R''. Here, R and R' are synonymous with R7 and R3, respectively, X' is synonymous with X, Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, Alkyl group, F In the formula, Re and R7 each represent water, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, and an alkenyl group. group or -B.

Alkyl groups, cycloalkyl groups, aryl groups, heterocyclic residues (including those in which 5- to 6-membered unsaturated rings are fused)
or represents an amino group, n, ~n6 and m + ”
ms each represents an integer from 1 to 6.

and R6 may each represent -B-SZ, and R and R3, R and R', and R and R2 may each be bonded to form a ring.

Note that the compound represented by the formula also includes ethanolated compounds and salts thereof. General formula [m] where Zl represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, an N-containing heterocyclic residue, or -S-B, -Y. n represents an integer from 1 to 6. ] General formula []V] [In the formula, Rs and R represent each, and R+11 is an alkyl group or -(CHt)nss
Represents Os e. (However, R3° is -(CH1)ns S
When Os θ, Q represents 0, and when it is an alkyl group, l
represents. )GO represents an anion. n11 represents an integer from 1 to 6. General formula [V] represents a vinylene group, and q3, ql, q, and q4 are each 0. Represents I or 2. Further, the ring formed with the yellow atom may be further condensed with a 5- to 6-membered saturated or unsaturated ring. ] General formula [■] [In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings or saturated rings are condensed), R11 is a hydrogen atom, and Q' has the same meaning as Q. ] General formula [■Rr* RI2 R+5 [In the formula, X is -COOM' -OH.

-S Os M', -CON Ht, S
Ot N H2.

NH2, -9H, -ON, -Co, R, .

-8O2R,6,-OR,,,N R18RI? .

-S R, , -S O, R, 11, -N HCOR,
,.

N1(SO*R+e, -0CORre or -5OtRI
a represents Y, a bond, an alkylene group having 1 to 8 carbon atoms, or Rls
R13RI2 or a hydrogen atom, m and R8 are each 1 to 10
represents an integer. RIll RIt, Rla+ R+s
7 and R1 are each a hydrogen atom, a lower alkyl group, an acyl group, or R25 and ]" (28 each represents a hydroxy-substituted lower alkylene group, X and y each represent 0 or l, and G' represents an anion. and Z represents 0.I or 2.] Represents a kill group and %RII is -NR, .Rtlx ORt
2 or -5Rtt, R2I and R2 each represent a hydrogen atom or a lower alkyl group, and R22 is RIl
Represents the atomic group necessary to combine with l to form a ring.

R7° or R21 may be combined with R+a to form a ring. M' represents a hydrogen atom or a cation. ] General formula [X
] (H)x (a・)z (II)y In the formula, Ar is 2
Represents a divalent organic group consisting of a valent aryl group or a combination of an aryl group and an oxygen atom and/or an alkylene group, and B! and B each represent a lower alkylene group,
In the formula n25, R24, 1, R6 and R3o each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group Table 17.1) 1. represents a hydrogen atom or an alkyl group,
R1, represents 71 (represents an elementary atom or a calhoquine group. 1 The compounds represented by the general formulas [13 to [lX]) preferably used in the present invention are compounds generally used as bleaching accelerators, and hereinafter, It is called a bleach accelerator.

Typical specific examples of the bleaching accelerators of the present invention represented by the general formulas [+] to [IX] include, but are not limited to, the following.

Exemplary compound (+-3) (]-9) (+-6) C)l, C1l, C00H C)1. C1l,COO)I (■ l) 'D -2) (■ (It (n-5) 11:C-!1lI-C-NH-!ill -C-N1
1- CI+2S (■ ]1) (Il (mouth (n-15) (It-6) H,N-C3llIIliHCS-Nl11(■ HtN C3NII(C1ty)-NIIC3NHy
(II -8) (It -9) (II-IO) (II-16) (■ (It-18) (II-19) (II-20) (II (II (III) (In (Ill mark (m) -4) (lII (old-10) (II-26) (It-27) (m-11) (■ (lII-14) (■ (■ (■ +2) (V-14) (V-9) (V-11) If) If (V-13) (V-1) (■ (V-6) (■ ]5) (V-16) (V (V (■ (V-7) (■ 2) ) (V -22) (\) 8"γN 1l (XRI(Nri(Xrl f011 (■ (■ 1・-ノ(■ (■ (■ (■ ('i'l-7) (■ ri (Xri January) (■-1) (■ (■-3) (■ (■-5) (■-6) (■ ri (Vl-6) ()'l -9) () ri ( ■-7) (■-8) (■-9) (■-10) (■-11) (■-12) (X'1 C!IJ (CII, CII, 0Il).

(X pieces (Xl CILti(CIItCIl-011)t(■ !l5C11, CH2NCII□CII 2C0111
1! (■-14) 113GHzc) 12NHclbclI2011 (■-
15) +1SC112CH, NC11, CH, 0HC211° (■-4) C11, N (CI1, CI, OH).

Φ C1l t N (C1l t C1l yellow)
z(IX-1) (IX-2) (IX-3) (IX-4) (iX-5) In addition to the bleaching accelerator of the present invention exemplified in the margin 1 below, Patent Application No. 111
'(6(] -263568-', ', Ming 411 i!
; (rJ No. 5 Illustrative compound! IJFJNo, I-
2, I-4 to 7, I-9 to 13, ■-16 to 21, knee 23, ■-24, l-26.

27,■-30~36,I-:18,ll-2~5,U
-7~10, ll-12~20, ll-22~25, ■
-27, -29~33, ll-35.36, ll-3
8-41, 1Ii3, II-/15-55, ll-57
~60, ll-62~64, IT-67~7L H73
~79, ll-81~84, ll-86~99,
ll-101, 102, ll-104 to 110, ll-
112-1]9, ll-121-124, H-125,
11i28~144, ll-145, 11-148~
]55, 11-157, m-4, lll-6 ~8.
11I-10. 11. m-13, -15 to +8.
m-20. lll-22, ■-23, ■-25,
lll-27, ■-29 to 32, [-35. 36, I
V-3, TV-4, -3 to 6, V-8 to +4,
V-16~38, ■-40~42, ■-44~
46, ■-48~66, ■-68~70, V-72
~74, V-76 ~79, V-81. 82, V8
4~! 00, V-102 ~10g, V-11 [+,
V-112, 113, V-116 ~ 119, V-12
1 ~ +23, V-125 ~ 1:10, V-132
~+44, V-146 ~+62, V-164 ~17
4, V-176 ~ 184, Vl-4, Vl
-7, ■-10, ■-12, ■~13, ■-16,
Vl-19. ■～21. VT-22Vl-25
．． Vl-27~34. VI-36, ■-3, ■-6■-
Compounds such as No. 13, ■-19, and VIA-20 can also be used in the same manner.

These tF! The white accelerator may be used alone.

Two or more types may be used in combination, and good results can generally be obtained when the amount added is in the range of about 0.01 to 100 g per In of the bleach-fix solution. However, if the amount added is too small, the effect of promoting bleaching will be small, and if the amount added is too large, precipitation may occur and contaminate the silver halide color photographic material being processed. Because there is, 1 sentence of bleach-fix solution! 1.115 to 50g is preferred, more preferably bleach-fix solution 1! ; 0.05 to 15 g per L.

When adding a bleach accelerator, it is generally possible to add and dissolve it as is, or to dissolve it in water, alkali, organic acid, etc. before adding it. It can also be added after being dissolved using an organic solvent.

After the treatment with the fixing solution or bleach-fixing solution, a normal water washing treatment may be performed, or in particular, in the present invention, it is preferable to perform a stabilization treatment without substantially including a water washing step.

In the present invention, stabilization treatment that does not substantially include a water washing process means that immediately after treatment with a treatment liquid that has fixing ability, a water washing alternative stabilization treatment is performed using a single tank or multiple tank countercurrent method, etc. , rinsing, auxiliary water washing, and known water washing promotion baths may also include treatment steps other than general water washing.

In the stabilization treatment step of the present invention, the method of bringing the stabilizing solution into contact with the silver halide photosensitive material is preferably by immersing the silver halide photographic material in a bath as in a general processing solution. Synthesis M! [It may be applied to the emulsion surface of the silver halide photographic light-sensitive material, both sides of the conveyance leader, and the conveyance belt with a cloth or the like, or it may be sprayed with a spray or the like. Below, we will mainly explain the case where a stabilizing bath using the immersion method is used.

It is preferable that the stabilizing liquid L contains a chelating agent having a chelate stability constant of 6 or more with respect to iron ions.

Examples of the chelating agent having a chelate stability constant of 6 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe:l + ).

Specific examples of chelating agents having a chelate stability constant of 6 or more with ferric ions include diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and the like.

The amount of the above chelating agent used is 0.01 to 0.01 per liter of stabilizing solution.
50g, preferably in the range of 0.05-20g.

Furthermore, preferred compounds to be added to the stabilizing solution include:
Examples include anti-spill agents, water-soluble metal salts, ammonium compounds, and the like. The above-mentioned anti-piping agents include hydroxybenzoic acid compounds and phenol compounds.

Isothiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propatoolamine compounds, sulfamide compounds, amino acids Examples include penztriazole-based compounds and penztriazole-based compounds.

Furthermore, as metal salts, Ha, Ca, Ce, Go
, In.

La, Mn, Ni, Pb, Sn, In, T
Metal salts of Mg, An, and Sr are supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, and acetates, or as water-soluble chelating agents.

The amount used is lx 10-' per 11 stabilizers.
lX'lrho 1 mol, preferably 4x 1
0-' to 2x 10-' moles, more preferably 8X 1
The range is from 0-' to lx 10-2 moles.

In addition to the above compounds, the stabilizing liquid also contains optical brighteners, organic sulfur compounds, onium salts, hardeners, quaternary salts, water droplet prevention agents such as polyethylene oxide derivatives, siloxane derivatives, etc.
pH adjusters such as boric acid, citric acid, phosphoric acid, acetic acid, or sodium hydroxide, sodium acetate, potassium citrate,
Organic solvents such as methanol, ethanol, dimethyl sulfoxide, dispersants such as ethylene glycol and polyethylene glycol, and other color tone adjusting agents improve processing effects.
Addition of various additives for expansion is optional.

The above compounds and other additives can be added to the stabilization tank as a concentrated liquid, or the above compounds and other additives may be added to the stabilizing liquid supplied to the stabilization tank and then stabilized. There are various methods, such as using it as a supply solution for the stabilizing solution, or adding it to the pre-bath of the stabilization treatment process and making it present in the stabilization tank by including it in the silver halide photographic light-sensitive material to be processed. It may be added by such an addition method.

As for the method of supplying the stabilizing liquid in the stabilization treatment step, when a multi-tank countercurrent system is used, it is preferable to supply the stabilizing liquid to the rear bath and overflow from the front bath.

The pH value of the treatment liquid in the stabilizing bath is preferably in the range of pH 4 to 8.

Further, the pH can be adjusted using the above-mentioned pl+adjusting agent.

The treatment temperature during stabilization treatment is 1, e.g. 20°C to 5
0°C1, preferably in the range of 25°C to 40°C. In addition, from the viewpoint of rapid processing, a short treatment time is preferable, usually 20 seconds to 5 minutes, most preferably 30 seconds to 2 minutes, and in a multi-vessel countercurrent method, how long should the pre-stage be treated? ,
It is preferable that the post-stage treatment time be longer.

In the present invention, there may be no need for washing with water before and after the stabilization treatment, or the surface may be cleaned by rinsing with a small amount of water within a short period of time or by using a sponge, stabilizing the image, and improving the surface properties of the silver halide photographic light-sensitive material. Providing a treatment tank for adjustment is optional. For stabilizing the above-mentioned image and adjusting the surface properties of the silver halide photographic light-sensitive material, activators such as formalin and its derivatives, siloxane derivatives, polyethylene oxide compounds, quaternary salts, etc. are listed.

In the present invention, it is optional to provide additional processing steps in addition to the above processing steps. In addition to the above-mentioned stabilizing solution, silver may be recovered by a known method from a processing solution containing a soluble silver complex salt, such as a fixing solution, a bleach-fixing solution, or a bleach-fixing solution.

Furthermore, if the above-mentioned stabilization treatment is carried out, a washing process is essentially unnecessary, and therefore, there is no need for pipes or sinks for washing, and there is an advantage that the apparatus itself can be easily installed at any location.

In addition to these treatments, there is a method in which the developer produced by color development is halogenated and then subjected to i1f 1 layer color development, and various intensifying treatments (amplification) described in the specification of JP-A-58-154839. Processing may be performed using a developing method that increases the produced color Jj-, such as processing).

Each processing step is usually carried out by immersing the photosensitive material in a processing solution, or by other methods, such as a spray method that supplies the processing solution in the form of a spray, or by contacting it with a carrier impregnated with the processing solution. A web method using viscous development processing, a method using viscous development processing, etc. may also be used.

The internal latent image type (inner layer type) silver halide emulsion used in the present invention is an emulsion having silver halide grains that mainly form a latent image inside the silver halide grains and have most of the photosensitive nuclei inside the grains. This includes any silver halide such as silver bromide, silver chloride, silver iodochloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like. Among them, silver chloride, silver chlorobromide, silver chloroiodobromide, and silver iodochloride are preferred from the viewpoint of grains having a high development speed, and silver chloride and silver chlorobromide are particularly preferred.

An internal latent image type silver halide emulsion in which the grain surface is not predispersed means that the emulsion used in the present invention is coated on a transparent film support at a ratio of 15 mg/cm to n'. The density obtained when the test piece was developed with the following surface developer A at 20°C for 10 minutes without being exposed to light was 0.6.
Preferably, it does not exceed 0.4.

Surface developer A Metol 2.5g Dan-ascorbic acid 10g NaBO2・41120 35gKRr
Add 1 g of water to IM.Also, the silver halide emulsion according to the present invention can be prepared using internal developer B of the following formulation after exposing the test piece prepared as described above.
It gives sufficient density when developed with.

Internal developer B Metol 2g Sulfite sorter (anhydrous) 90g Hydroquinone 8g Carbonate sorter (-hydrate) 52.5gKBr
5gK1
To be more specific, a portion of the specimen was exposed to a light intensity scale for a defined period of time up to approximately 1 second, and then exposed to a light intensity scale using internal developer B. when developed for 10 minutes at 20°C, at least 5 times, preferably at least 5 times, that obtained when another portion of the specimen exposed under the same conditions was developed in surface developer A for 10 minutes at 20°C. It exhibits at least 10 times the maximum concentration.

It is preferable that the internal latent image type silver halide grains used in the present invention are not chemically sensitized on the surface of the grains, or are sensitized only to a small extent.

The silver halide emulsion used in the present invention may be a core-shell emulsion consisting of a core and at least one shell covering the core. In this case, it is preferable from the viewpoint of rapid processing that the surface composition of the shell contains at least silver chloride, and in particular, the silver chloride content of the shell should be 10 mol% or more, preferably 30 mol% or more to achieve the present invention. It is particularly preferable to do so.

In the present invention, a photosensitive material using an internal latent image type (inner layer type) silver halide emulsion is processed.

After exposing (photographing) the photosensitive material in a conventional manner,
A positive image can be easily obtained directly by surface development using the color developing solution of the present invention. That is, the main step of creating a direct positive image is to fog the light-sensitive material of the present invention having an internal latent image type silver halide emulsion layer which has not been fogged in advance by a chemical action or an optical action after image exposure. It consists of performing surface development with the color developing solution of the present invention after and/or while performing a treatment for generating nuclei, that is, a fog treatment. Here, the fogging process can be carried out using a compound that provides full exposure or generates fogging nuclei, that is, a fogging agent.

In the present invention, the entire surface exposure is carried out by immersing or moistening the image-exposed photosensitive material in a developer or other aqueous solution, and then exposing the entire surface uniformly to light.

The light source used here may be any light within the wavelength range to which the photographic light-sensitive material is sensitive, and it may be a short-term exposure to high-intensity light such as a flash light, or a long-term exposure to low-intensity light. Good too. Further, the total exposure time can be varied over a wide range depending on the photographic material, development processing conditions, type of light source used, etc. so as to ultimately obtain the best positive image.

In the present invention, the support has two or more silver halide emulsion layers, each having a different sensitive wavelength range, and the silver halide is an internal latent image type silver halide emulsion which is not pre-fogged. When directly forming a positive image by exposing a silver halide color photographic light-sensitive material to light for one image, prior to development, or during the development process, the H of the full exposure for each of the silver halide emulsion layers is It is preferable to provide a full-surface exposure with a ratio of normal intensity of no greater than 6.

The illuminance for full-surface exposure, i.e., light fog, used in the present invention is preferably an illuminance that does not cause illuminance malfunction during light fogging, and may vary depending on the photosensitive material, but is generally 0 to 2000 lux, preferably 0.05 to 30 lux, More preferably, one having an illuminance of 0.1 to 5 lux can be used. This light fogging illuminance may be adjusted by changing the luminous intensity of the light source, or by using various filters to reduce the light, the distance between the photosensitive material and the light source, the angle between the photosensitive material and the light source, etc. In addition, to reduce light fogging exposure time,
It is also possible to use a method of fogging with weak light at the initial stage of exposure and then fogging with stronger light.

Further, as described in Japanese Patent Publication No. Sho 58-1172486, a method of exposing the entire surface to light while increasing the illuminance can also be advantageously carried out.

Exposure devices that can be used for full-surface exposure include Utility Model Application No. 10103, Utility Model Application No. 55-4132:1, Utility Model Application No. 59-87051, Utility Model Application No. 59-870521,
5l-fi 1542, patent application 1982-2:15] 65
The device described in the above can be used advantageously.

A wide variety of compounds can be used as the fogging agent used in the present invention, and this fogging agent only needs to be present during the development process, for example, in constituent layers other than the support of the photographic material (among them (particularly preferably in a silver halide emulsion layer), or may be contained in a developing solution or a processing solution prior to development processing. The amount used can be varied over a wide range depending on the purpose, and the preferred amount is 1-1500 Il 1 g, preferably 1-1500 Il 1 g per 1 mole of silver halide when added to a silver halide emulsion layer.
It is 1000 mg. When added to a processing solution such as a developer, the preferred amount is 0.01 to 5 g/u, particularly preferably 0.05 to Ig/u.

Examples of fogging agents used in the present invention include 1, for example, U.S. Pat.
563,785, hydrazines described in 2,588,982, or U.S. Pat. No. 3,227,5
Hydrazide or hydrazone compounds described in US Pat. No. 52; US Pat. No. 3,615,615, US Pat.
No. 9, same: I, No. 719,494, same No. 3,734,7:
18 and US Pat. No. 3,759.901; and US Pat. No. 4,030,925
such as the acylhydrazinophenylthioureas described in No.
Compounds having adsorption groups on the silver halide surface may be mentioned. Moreover, these fogging agents can also be used in combination.

For example, Research Disclosure (ResearchD)
No. 15162 describes the use of a non-adsorption type fogging agent in combination with an adsorption type fogging agent, and this combination technique is also effective in the present invention.

As the diluting agent used in the present invention, either an adsorption type or a non-adsorption type can be used, or they can be used in combination.

Specific examples of useful fogging agents include hydrazine hydrochloride,
Phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, l-formyl-2-(4-methylphenyl)hydrazine, 1-acetyl-2-phenylhydrazine, l-acetyl-2-(4-acetamidophenyl)hydrazine, ■-Hydrazine compounds such as methylsulfonyl-phenylhydrazine, 1-benzoyl-2-phenylhydrazine, l-methylsulfonyl-rusulmaldehyde phenylhydrazine, 3-(2-formylethyl)-2-methylbenzothiazolium Bromide, 3-(2-formylethyl)-2-propylbenzothiazolium furomite,
3-(2-acetylethyl)-2-pencylbenzoselenazolium furomide, 3-(2-acetylethyl)-
2-pencyl-5-phenyl-benzoxacilium bromide, 2-methyl-:l-[:I- (phenylhydrazino)propyl benzothiazolium furomite,
2-Methyl-3-[:I-(1helazino on p-tolyl)
Propyl benzothiazolium furomite, 2-methyl-3[:l-(p-sul]ophenylhydradino)brohyal]benzothiazolium furomite, 2-methyl-
3-[3-(p-sul]ophenylhydradino)pentyl]penzothiazolium iodeto, 1,2-dihydro-
3-Methyl-4-phenylpyrido[2,l-bl benzothiasorium turomite, 1.2-Schich F low 3-methyl-4-phenylpyrido[2,1-b]-5-phenylbenzoxacilium furomite, 4. 4'-ethylenebis(1,2-dihydro-3-methylpyride[2,1
-bl benzothiaturium furomite), 1.2-
Dihydro-3-methyl-4-phenylpyrido [2,I-
bl benzoselenazolium puromite etc. N-1 substituted quaternary
class cycloammonium 1; 5-[1-ethylnaphtho(1.2-b)thiazolin-2-ylideneethylidene]
-1-(2-phenylcarbazoyl)methyl-3-(4
-sulfamoylphenyl)-2-thiohydantoin,
5-(3-ethyl-2-benzothiasolinyllane)-
3-[4-(2-]ormylhydrazino)phenyl]rotanine, l-[4-(2-]ormylhydrazino)phenylcoco-phenylthiourea, 1,3-his[4-(
2-]Oormylic hydrazinophenylcothiourea and the like.

In addition, other fogging agents that can be effectively used in the present invention include the general formulas [N-I], [
N-II]. Specific examples of these include compounds (1) to (79) described in JP-A-63-106656, pages 21 to 27.

The silver halide emulsion according to the present invention may contain a wetting agent, a film property improver, a coating aid, a gelatin plasticizer, a surfactant, an ultraviolet absorber, a pH adjuster, an antioxidant, etc. depending on the purpose. 1″
Various photographic additives such as electric protection IF agents, thickeners, graininess improvers, dyes, Mortacyto 1 brighteners, development rate regulators, matting agents, etc. can also be used.

The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer and a filter layer as required to obtain an internal latent image type light-sensitive material of the present invention.

It is useful to use the light-sensitive material of the present invention for full color use, and in this case it is preferable to include cyan, macenta and yellow dye-forming couplers in the silver halide emulsion.

Among these, yellow dye-forming couplers include hensoylacetanilide type and hivaloylacetanilide type couplers, and macenta dye-forming couplers include 5-
Pyrazolone type, birasolinohensimidazole type, and intazolone type couplers may be used within the range that does not impair the effects of the present invention. Cyan dye-forming couplers include phenol, naphthol, and virazoloquinasolone couplers.

In the present invention, the JIQ formula (M-I
) (For specific examples of these macenta couplers, see Toku DF4, 83-1066.
No. 55 specification, pages 29 to 34, No. 1 to No.
, 77 can be mentioned. ) A cyan coupler represented by the general formula (C-1) or (C-II) also described on page 34 (Specific examples of cyan couplers include:
On pages 37 to 42 of the same specification, a) (C'-1) ~ (
C′-82), (C″-1) to (C″-36). ), high-speed yellow couplers also described on page 20 (specific examples of yellow couplers include (Y'-1) to (Y'-3) described on pages 21 to 26 of the same specification).
9) Can be mentioned. ) is preferably used in combination with the photosensitive material of the present invention from the viewpoint of the desired effects of the present invention.

In addition, in order to prevent color fading of dye images due to short-wavelength actinic rays, it is useful to use ultraviolet absorbers, such as thiasolitone, penntriazole, acrylonitrile, and benzophenone compounds.
It is advantageous to use Ciba Geigy 320, Ciba Geigy 325, Ciba Geigy 327, and Ciba Geigy 328 alone or in combination.

Any support may be used for the photosensitive material used in the present invention.
Examples include carefully subbed polyethylene prephthalate film, polycarbonate film, polystyrene film, PP propylene film, cellulose acedate film, glass, baryta paper, and polyethylene laminate paper.

In addition to gelatin, the light-sensitive material used in the present invention may contain a suitable gelatin derivative as a protective colloid or binder depending on the purpose. Suitable gelatin derivatives include, for example, acylated seratin, quanisylated seratin, carbamylated seratin, cyanethanolated seratin, and esterified gelatin.

In addition, in the present invention, depending on the purpose, other wood-loving binders may be included in the emulsion layer or the emulsion layer or intermediate layer, protective layer, filter layer,
It can be added to the constituent layers of the photosensitive material such as a backing layer depending on the purpose, and the above-mentioned wood-philic binder can also contain a suitable plasticizer and lubricant depending on the purpose.

Further, the constituent layers of the photosensitive material 1 of the present invention can be hardened using any suitable hardening agent. These hardeners include chromium salts, zirconium salts, aldehyde groups such as polyaldehyde and mucohalogen acids, halotriazine-based hardeners,
Examples include polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners.

The photosensitive material used in the present invention can be effectively applied to various uses such as general color use, false color use, printing use, micro use, silver dye bleaching use, and colloid transfer method,
Rochas U.S. Pat. No. 3,087,817, ibid.
185,567 and 2.98:1,606, U.S. Pat. No. 3,253,915 to Weyertz et al., U.S. Pat. , 551, Whitemore, U.S. Pat. No. 13,227,552, and Rand et al., U.S. Pat. It can also be applied to color image transfer methods, color diffusion transfer methods, absorption transfer methods, etc.

[Effects of the Invention] According to the present invention, stains and fog caused by adhesion of dyes eluted from light-sensitive materials and dyestuffs to processed light-sensitive materials are improved even when replenishment is low, and photographic properties are stable over a long period of time. In addition, it is possible to provide a processing method for photosensitive materials that can be processed using the following methods, and furthermore, it can prevent fluctuations in the minimum density (D+++in) during ink processing, and reduce the maximum density (Dmax) while maintaining the stability of the color developing solution. The present invention provides a method for processing photosensitive materials that prevents this.

[Examples] The following are examples of the present invention, but the present invention is limited to these:
Not j2.

Example 1 The inner layer and emulsion (Em-1) were prepared as follows.

An aqueous solution containing gelatin was controlled at 50°C, and then an aqueous solution of silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KRr:NaCl = 60:411) was added to a controlled temperature of 50°C. By adding at the same time, the average particle size is 0. :18pm cubic emulsion a)
is. Sodium thiosulfate and potassium chloroaurate were added to the core emulsion thus prepared (1) and heated at 55°C.
Chemical ripening was performed for 20 minutes. This emulsion is called Emulsion A.

An aqueous solution containing emulsion A as a core and an aqueous silver nitrate solution, potassium bromide and sodium chloride (in molar ratio KB
r:NaC ratio=20:80) was added at the same time to obtain tetradecahedral particles with an average particle size of 0.48 gm. This emulsion is emulsion F.
shall be.

Sodium thiosulfate was added to this emulsion F to perform chemical sensitization, and after completion of the chemical sensitization, 9B of 1-phenyl-5-mercaptodetrasol was added per mole of silver halide.

A photographic material shown in Section 1 was prepared using the inner layer type emulsion (Em-1).

[Preparation of internal latent image type photosensitive material] On a paper support laminated with polyethylene, each of the layers described above was coated from the support side to prepare an internal latent image type photosensitive material (Test t1).

1st layer Cyan-forming red-sensitive silver halide emulsion layer Cyan coupler, 2,4-cyclo-3-methyl-5[α-(2
,4-C-Lcrt-amylphenoxy)phthylamide 1
Hecotenol 92g, 2,5-sheet tCrt-octylhy 1-3g quinone, tricresyl phosphate 5
0 g, paraffin I 8: Mix and dissolve Ig and 48 g of ethyl acetate, add gelatin solution containing sodium dodecylbenzene sulfonate, and add 3.0 g of sensitizing dye ([) per mole of silver halide. An internal layer image-type silver halide emulsion (Em-1) sensitized with 10-' mole of Ox was added, and silver 'Hf
4001g/m', AI dyed book 4 [I 17mg/m',
Coating was carried out so that the coupler cap was 330 tg/rrf.

2nd Layer/Intermediate Layer 100 nl of a 2.5% gelatin solution containing 4.5 g of gray colloidal silver and 8 g of 2,5-cyjert-octylhydroquinone dispersed in cyphthylphthalate was added to colloidal silver♀-:]85 mg/rrI ' was applied.

Third layer: Magenta forming green-sensitive silver halide emulsion layer Magenta coupler, 1-(2,4,6-1-lichlorophenyl)-:1-(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone 95g, 2,
Mix and dissolve 5 g of 5-sheet tert octyl hydroquinone, Sumilizer MDP (50 g of Sumima Kagaku Kogyo Co., Ltd.), 190 g of paraffin, 10 g of cyphthylphthalate, and 55 g of ethyl acetate, add a ceratin solution containing sodium dodecylbenzene sulfonate, and dissolve silver halide. An internal latent image type silver halide emulsion (Em-1) sensitized with 3.OX In-' moles of the sensitizing dye (11) per mole was added, the silver amount was 4101 ng/rn', and A I dye [II
] 181g/m', coupler cap 390m g
/ So that it becomes m'? I did it.

Fourth layer, yellow filter layer A 2.5% seratin solution containing 1-5 g of yellow colloid and 5 g of 2,5-sheet tert-octylhydroquinone dispersed in cyphthylphthalate was mixed with colloidal silver or 2.
00+ng/m'.

5th layer: yellow-forming blue-sensitive silver halide emulsion layer yellow coupler, α-[4-(1-hensyl-2-phenyl-3,5-dioxo-1,2,4-triasolicinyl-α-hyhalyl-2- Chlorozu-[γ-(2,4-
Mix and dissolve 120 g of tert-amylphenoxy)butyramide] acetanilide, 3.8 g of 2,5-tert-octylhydroquinone, 190 g of paraffin, 15 g of Tinuhin (Chihakaiki Co., Ltd. V), and 70 ml of ethyl butyrate in siftyl cyphthyl phthalate. , dodecyl, and sensitized sulfone were added to the solution containing sodium resistant sensitizing dye [I] per mole of silver halide. Ox
IQ-'mol sensitized internal latent image type \logenization
[Add (milk?'T'l (E m -1), 394
'+(380+ng/m', coupler amount 400+ng/
It was applied so that it was m'.

6th layer, protective layer The gelatin amount was applied at 210 mg/m'.

Incidentally, all of the above layers contained saponin as a coating aid. In addition, as a hardening agent, 2,4-dichloro-6-hydroxyl S-)-riazine sodium was added to layers 2.4 and 6.
Each gelatin was added in an amount of 22 mg per Ig of gelatin.

Sensitizing Dye I Sensitizing Dye m [IJ Sensitizing Dye II I [IIj S(+3ω 02H 3OkoK ■ [IIr]) The above light-sensitive material sample was exposed through an optical wedge and then processed in the following steps.

The composition of each treatment liquid is as follows.

[Color developing solution] Mother liquor Pure water 800m Hydroxylamine conductor (listed in Table I) Potassium bromide Sodium chloride Potassium sulfate Triethanolamine Color developing agent [CD-1/CD-2='8 below] 2.5 g 0 .8g 1.0g 1.0g 2, Og 0.03mol diethylenetriaminepentaacetic acid potassium carbonate 2g Replenisher 800 [11 sentences 3.2g 0g 0.5g 1.5g 2.5g 0.035mol 3.5g 5g (fluorescence Whitening agent, manufactured by Nippon Yossosha) pH 10.2 pH 10.6 Add pure water to make 1M 20% potassium hydroxide or 10%
Adjust pl+ with dilute sulfuric acid.

D 0・”・\10・1′・01 ■ N.H.

D 0.1.＼ノ.1.NB50.0B.Hm [f'5 White fixer Cofii liquid Pure water 550+o Edilenecyamine tetraacid iron (III) Ansenium salt Ammonium thiosulfate Sodium butyrosulfite Sodium metabisulfite Ethylene Cyamine Tetra Vinegar Di-Sodium 5g Replenisher 50ml 5g 2-amino-5-mercapto 1. Og 1.
2g+, :I, 4-thiacyasole pH 6,5 pH 6,2 Add pure water to make one layer, and add aqueous ammonia or dilute sulfuric acid to pH 6,2.
Adjust H to A.

[Water washing (+ stable solution) Mother liquor Replenisher orthophenylphenyl 0.2g 0.2g
Nor-Hydroxyethythelene 5,0 g5,0 g Syn-,1-diphosphonic acid (60% aqueous solution) An-7nia water 3.0 g 3.0
gpif 8.0 pH 8.0 Add water to make 1 mixture, ammonia water and sulfur "Cpl+"
Adjust.

A running test was conducted using an automatic developing machine using the exposed photosensitive material and the processing solution. The running test was carried out continuously until the total amount of replenishing color developer replenisher was twice the tank capacity of the color developer tank of the automatic processor. The above photosensitive material was processed using the processing solution after running test 1 to completion, and the clean reflection density of the lowest density portion was measured, and the difference between the start time and end time of the running test was determined. Furthermore, the clean reflection density at the highest density part of the running test was determined.

The results are summarized in Table 1.

Table 1 From Table 1 above, when the hydroxylamine derivative according to the present invention is used in a color developer and the replenishment amount in the color development step is within the range of the present invention, the green reflection degree C of the lowest density part is good; And it can be seen whether a sufficient maximum concentration can be obtained.

Example 2 The magenta coupler in the photosensitive material sample used in Experiment No. 1-:l of Example 1 was replaced with the bilan lotriazole type magenta described in JP-A-63-106655, pages 29 to 34. Couplers (M'-1), (M'-2), (M
'-4), (M'-21) (M'-37), (M'-6
1) and (M'-5:l) and conducted similar experiments, the maximum reflection density of the clean was approximately 0.1 higher than that of Experiment No. 1 of Example 1, I-:1. The difference in reflection density at the lowest density portion was 0.01, which was extremely good.

Example 3 A similar experiment was conducted using the sample and treatment liquid used in Experiment No. I-5 of Example 1. However, the processing time of the bleach-fix solution was set to 30 seconds, and the bleach-fix solution was added to the bleach-fix solution as shown in Table 2 above.
2g/l of bleach accelerator as shown in and 2g/l of color developer.
Experiments were conducted by adding 0% of each. Table 2 shows the results of the residual silver amount and magentastin (green reflection density at the lowest density part).

Table 2 As shown in Table 2 above, by using the processing method of the present invention in combination with a specific purulent whitening agent, the bleach-fixing processing time was shortened, the amount of residual silver was small, and magenta I know that Stain will also be in good condition.

Patent Applicant Konikka Stock Certification Association Chief Brewer Osamu Man Fill the slope with soil mouth Faith V3

Claims (1)

[Scope of Claims] A method for processing a silver halide color photographic light-sensitive material including a color development process, wherein the silver halide color photographic light-sensitive material supports at least one photographic emulsion layer containing internal latent image type silver halide grains. A photosensitive material that is coated on a body, wherein the color developer contains a compound represented by the following general formula [A], and the replenishment amount of the color developer is equal to or greater than 1.
A method for processing a silver halide color photographic material, characterized in that the amount is 0.1 to 2.5 ml per 00 cm^2. General formula [A] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_1 and R_2 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. However, R_1
and R_2 are never hydrogen atoms at the same time. Also, R_
1 and R_2 may form a ring.