CA1306895C - Method for processing silver halide photo-sensitive material - Google Patents

Abstract

ABSTRACT

Processing an imagewise exposed light-sensitive silver halide photographic material comprising a support having thereon at least one silver halide emulsion layer containing silver halide grains which are sensitized with a sensitizing dye represented by general formula [I]:

[I] (wherein, Z1 and Z2 independently represent a group of atoms necessary to complete a heterocyclic ring consisting of a thiazole, a benzothiazole, a selenazole, a benzo-selenazole, a naphthoselenazole, a benzimidazole, a naphtho-imidazole, a pyridine or a quinoline ring, wherein said heterocyclic ring may have a substituent; R1 and R2 are independently selected from a group consisting of an alkyl group, an alkenyl group and an aryl group; R3 is selected from a group consisting of hydrogen atom, a methyl group and an ethyl group; X1 is an anion and 1 is 0 or 1).
Processing takes place with a color developer solution containing an aromatic primary amine color developing agent in the presence of at least one hydroxylamine derivative represented by general formula [II] or a water soluble acid salt thereof:

[II]

Description

METHOD FOR PROCESSING SILVER HALIDE PHOTO-SENSITIVE MATERIAL

FIELD OF THE INVENTION
The present invention relates to a method for processing silver halide photo-sensitive materials, in particular to a method for fast and stably processing silver halide photo-sensitive materials capable of preventing fog from increasing.
BACKGROUND OF THE INVENTION
In general, a silver halide color photo-sensitive material is provided with three kinds of silver halide color emulsion layer each selectively and spectrometrically sensitized so as to be sensitive to a blue light, a green light and a red light, respectively, applied on a support member. For example, a color negative photo-sensitive material is generally provided with a blue light-sensitive emulsion layer, a green light-sensitive emulsion layer and a red light-sensitive layer ap-plied in this order from a side exposed. A bleachable yellow filter layer is disposed between the blue light-sensitive emul-sion layer and the green light-sensitive emulsion layer to 1~6~

absorb a blue light passing through the blue light-sensitive emulsion layer. In addition, each emulsion layer is provided with other intermediate layers and a protective layer as the outermost layer for achieving various kinds of special object.
Besides, for example a color printing paper photo-sensitive material is generally provided with a red light-sensitive emul-sion layer, a green light-sensitive emulsion layer and a blue light-sensitive emulsion layer applied in this order from a side exposed. In addition, the color printing paper photo-sensitive material is provided with an intermediate layer, a protective layer and the like in addition to an ultraviolet ray-absorption layer for achieving a special object, respec-tively, in the same manner as in the color negative photo-sensitive material. It has been known that these emulsion layers can be arranged in a manner other than the above des-cribed. It has been known also that a sensitive emulsion layer consisting of two layers having a sensitivity in the substan-tially same wave length range to a light of each color is used as the emulsion layer. For these silver halide photo-sensitive materials for example a aromatic primary amine color developing agent is used as a color developing agent. Silver halide par-ticles exposed are developed and a reaction between an oxidized product of the color developing agent and a dye forming coupler leads to the formation of a dye image. In this method, in gen-eral, in order to form a cyan, magenta or yellow dye image, a ~3~9~

cyan, magenta or yellow dye-forming coupler is used, respec-tively.
Recently, a silver halide color photo-sensitive material (hereinafter referred to as a color sensitive material), which can be fast and stably processed, giving a high image quality, and being inexpensive, has been desired. In particular, a fast processable silver halide color photo-sensitive material has been desired.
That is to say, a siiver halide photo-sensitive material has been subjected to a running process in an automatic devel-oping machine placed in each developing shop but it has been required to develop and return the silver halide photo-sensitive material to a user within its receipt date as one of improved services for the user. Recently, it is being required even to return the silver halide photo-sensitive material to the user within several hours from its receipt. Thus, the rapid devel-opment of an increasingly fast processable silver halide color photo-sensitive material is being desired.
Although in general the formation of such a dye image com-prises a color developing process, a bleaching process, a fix-ing process (or a bleach fixing process) and a washing process of an exposed color sensitive material, it is considerably im-portant in respect of technique and practical use for a color printing paper requiring a particularly fast processability to shorten a time required for the color developing process.

~3~,'61~35 In order to speedily carry out the color developing proc-ess, measures, such as a raise of developing temperature, a reduction of a concentration of a bromide ion, which is a main ingredient of a development inhibitor, a raise of a concentra-tion of a color developing agent and a raise of pH, have been most usually taken.
The speed-up of the color developing process can be achieved also by processing a silver halide photo-sensitive material containing silver halide particles substantially com-prising silver chloride in the presence of a bromide ion in a color developer.
~ owever, in the event that the speed-up of the color de-veloping process is carried out by the above described various kinds of measure, a problem occurs in that a slight change of conditions (temperature, pH, time and the like), a slight change of composition (concentration of bromide ion and concen-tration of a color developing agent) and contamination of a minute amount of bleach fixing solution are apt to cause fog-ging.
On the other hand, recently it has been remarkably desired to remove benzyl alcohol as a dye formation-improving agent from a color developer in vie~ of pollution control. If benzyl alcohol was removed from the color developer, a dye formation speed is reduced. That is to say, the color developing agent develops exposed silver halide particles, whereby a reacting capacity betweent he resulting oxidized substance of the color developing agent and a coupler is suddenly lowered to be dif-ficult to obtain a high color.
It was found that such a problem (the reduction of color concentration) occurring in the event that benzyl alcohol was removed was particularly due to hydroxyl amine salt used in the color developer as a usual preservative.
It has been known that in the usual color developer the above described hydroxyl amine salt serves as a superior pre-servative for preventing the color developing agent from being oxidized with an air particularly in the event that it is used together with sulfite salts. Moreover, in the event that a color sensitive material was processed with a color developer containing benzyl alcohol at pH of akout 10, its influence upon the coloring capacity was remarkably small.
However, since hydroxyl amine peculiarly reduces the color concentratoin in the event that the developing process is car-ried out with a color developer without containing benzyl alco-hol, a method of fast color developing capable of reducing bad influences upon the maximum density and the gradation by using other preservatives in place of hydroxyl amine is necessary.
On the other hand, some preservatives for the color devel-oper have been proposed in place of hydroxyl amine. Among them hydroxyl amine derivatives having at least one substituent to the nitrogen atom are useful as a compound having a sufficient J6~"~5 preservatlve capaci-ty without extremely reducing the coloring capacity even in the event that the concentration of color de-veloper is sufficiently high and benzyl alcohol is not con-tained.
However, on the other hand, if such hydroxyl amine deriva-tive is used in place of hydroxyl amine as a preservative in the event that the process is carried out with a color develop-er without containing benzyl alcohol, a dye image of a silver halide photo-sensitive material can reach the maximum density quickly but a disadvantage occurs in that the fog is apt to be generated when the dye image of the silver halide photo-sensi-tive material reached the maximum density.
It has been known that mercapto compounds are preferably used as a fog inhibitor. Although mercapto compounds are ef-fective as a fog inhibitor, they exihibit no sufficient effect in an inhibition of such the fog that is apt to be generated in the event that the color developing process was speeded up in the above described manner.
SUMMARY OF THE INVENTION
The present invention was achieved in view of the above described state of art. Thus it is an object of the present invention to provide a method for processing a silver halide photo-sensitive material in which a pollution load is reduced by removing benzyl alcohol from a color developer and a dye image can be fast formed by carrying out a color developing 13~ 68~r3~;

process in the presence of a specific hydroxyl amine derivative, hereby restraining fog, with a reduced sensitivity or gradation fluctuation due to a change of pH.
Thus the present invention specifically relates to a method of processing a light-sensitive silver halide photo-graphic material which comprises a step of processing an image-wise exposed light-sensitive silver halide photographic mate-rial comprising a support and, provided thereon, at least one silver halide emulsion layer containing silver halide grains which are sensitized with a sensitizing dye represented by general formula [I];
[I]
Z ~ "-Z 2~
~ C C~ ...

R, R2 (X,(3)Q

(wherein, Zl and Z2 are independently represent a group of atoms necessary to complete a heterocyclic ring consisting of a thiazole, a benzothiazole, a selenezole, a benzoselenazole, a naphthoselenazole, a benzimidazole, a naphthoimidazole, a pyridine or a quinoline ring, wherein said heterocyclic ring may have a substituent; Rl and R2 are independently selected from a group consisting of an alkyl group, an alkenyl group and an aryl group; R3 is selected from a group consisting of hydro-gen atom, a methyl group and an ethyl group; Xl is an anion and 3~

R is 0 or 1); with a color developer solution containing an aromatic primary amine color developing agent in the presence of at least one hydroxylamine derivative represented by general formula [II] or a water soluble acid salt thereof;
[II]

N - OH

(wherein, R21 and R22 are independently selected from a group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms which may have a substituent provided that R21 and R22 are not simultaneously hydrogen atoms and that R21 and R22 may be combined with each other to form a nitrogen-containing ring);
and at least one nitrogen-containing heterocyclic mercapto-compound.
DETAILED DESCRIPTION OF THE INVENTION
Heterocyclic rings expressed by Z1, Z2 in said general formula [I] preferably include a thiazole-, a benzothiazol-, a naphthothiazol-, a selenazol-, a benzoselenazol- and a naththoselenazol ring, more preferably a thiazole-, a benzo-thiasol-, a selenazol- and a benzoselenazol ring, and most pre-ferably a benzothiazol ring.
These rings may be substituted by various kinds of substi-tuent, preferably halogen atoms, a hydroxyl group, a cyano 13~t~

group, aryl groups, alkyl groups, alcoxyl groups or alcoxycar-bonyl groups, more preferably halogen atoms, a cyano group, aryl groups, alkyl groups of Cl to C 6 or alcoxyl groups of C
to C6, and most preferably halogen atoms, a cyano group, a methyl group, an ethyl group, a methoxy group and an ethoxy.
Rl and R2 are alkyl groups, alkenyl groups or aryl groups.
However, alkyl groups expressed by Rl and R2 preferably include alkyl groups of Çl to C6, and most preferably an ethyl group, a propyl group and a butyl group. These alkyl groups may be sub-stituted by various kinds o. substituent, preferably a carbo-xylic group and a sulfonic group. In this case, salts may be formed between them and alkaline metal ions and an ammonium ion. At least one of Rl and R2 is preferably an alkyl group substituted by a sulfonic group. The alkenyl groups include an allyl group while the aryl groups include a phenyl group and the like.
R3 is a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom.
X ~ is an anion, preferably a chloride ion, a bromide ion, an iodide ion and a p-toluene sulfonic acid ion.
Q is an integer of O or 1. In addition, Q is O in the event that at least one of Rl and R2 is a group having a minus electric charge itself such as a carboxylic group and a sulfo-nic group.
Typical examples of a sensitizing dye expressed by the 13~6~

general formula [I] are below described but they are not re-strictive.

(I - 1) , ~ ~3 ~ C H ~ ~

(CH2)aS 03H
(CH2)3S 03(~) (I - 2) ~3 ~ C H ~< ~[3 (CH2)20 H
(CH2)aS Oa 13(~6~3~3 (I - 3) J~(~)N ~ =< N ~lC H 3 (CH2)~S O~Na (CH2)2S 0 ~) I - 4) C H=< ~

(CH2)~S 03H
(( ,H2)3S 03~) I - 5) ~63N~ C =<N ~

CH2CH=CH2 (CH2)2 ICHCH3 l~U~3~, H 3 C OJ~ N N ~0 C H 3 (CH2)3S 03Na (CH2)3S 03 (I - 7) C Ha< ~[3 (CH2)3SO3H N(C2Hs)3 ( C H 2 ) 3 S O 3 (I - 8) C H 3~

(CH2)2COOH
(C~12)2COO

13~.. 6~t~

(I - 9) ,~S e~ =<S e~C O O C 2 H s (CH2)2CHCH3 (CH2)2CHCH3 S 03Na S 0 3~) (I - lO) H 3 C 0~ N~ N~C H 3 (CH2)2S 03Na (CH2)2S 03(~) (I - 11) ~9N~ =<N~[3 C2Hs (CH2)~S 03 ~31~6~3''`3~
-- ~4 --(I - 12) C H=~<

C2Hs (CH2)~S 03 ( I - 13~

~S e~ =,<S e~`C H 3 C2Hs C2Hs Br(~3 (I - 14) ( C H ~ ) ~ S O ~
(CH2)2SO~H N(C2Hs)3 13~l65895 (I - 15) C H=l< ~

(CH2)2S 03H
(CH2)2S o3(3 (I - 16) H 3 C OJ~N I ~C H 3 (CH2)3S03H N(C2Hs)3 (CH2)3S 03(~) (I - 17) C.~J~N N~3 (CH2)3S 03H
(CH2)3S 03~) 8~'3S

(I - 18) C.~J~N ~~C~
(CH2)3SOaH N(C2Hs)3 (CH2)3S 03 (I - 19) C H=< ~

(CH2)2S 03H N (C2Hs)3 (CH2)3S 03 ~L3a6~9~

( I - 20) C H=~ ~

(CH2~2S 03H
(CH2)3S 03~) (I - 21 ) C H =< ~

(CH2)3S 03(~) (I - 22) 3~C H=< ~3 (CH2)3S 03 868~

(I - 23) H 0 C~ N N ~C

(CH2)3S 03 (I - 24) C H=< ~
CH2COOH~ N(C2HS)D
(1H2)2S O ~' 13~:t6~S

The sensitizing dye expressed by said general formula [I]
according to the present invention can be easily synthesized in accordance with methods disclosed in for exmaple sP 660,408 and USP 3,149,105.
In order to add the sensitizing dye expressed by said general formula [I] according to the present invention to a silver halide emulsion, the sensitizing dye is preferahly dis-solved in organic'solvents, such as methanol and ethanol, which can be optionally blended with water.
The sensitizing dye may be added in every step of the process of manufacturing an emulsion, preferably in the chemi-cal ageing step. In addition, a quantity of the sensitizing dye to be added is depend upon a kind of the sensitizing dye and a kind of the silver halide emulsion but the sensitizing dye is preferably added at a ratio of 0.01 to 0.5 g based on one mol of silver halide.
Although the hydroxyl amine derivatives used in the pre-sent invention are preferably added to the color developer solution, a system, in which the hydroxyl amine derivative of the present invention is previously incorporated in the sensi-tive material and the hydroxyl amine derivative of the present invention is supplied in the color developer by continuously processing the sensitive material, is also possible.
The hydroxyl amine derivative represented by general for-mula [II] inculdes, as preferable and non-limitative example ~ 3~68~35 those compounds listed below:
(II - 1)CH~ (II - 2) CH~

CH~ - N - OH C2Hs - N - OH

(II - 3)C2Hs (II - 4) CH~

C2Hs - N - OH ( iso)C3H7 - N - OH

(II - 5)C2Hs (II - 6) C~H7 (n)CJH7 - N - OH (n)CJH7 - N - ON

(II - 7)CHJ (II - 8) C2Hs H - N -OH H - N - OH

(II - 9)C2H~OH (II - 10) I CH2 ~ CH2 \
CHs ~ N ~ OH I N - OH

(II - 11) i so-C3H~ \
N - OH
iso-C~H7 /

~3~6~3~:~

(II - 12) (II - 13) C2Hs ~~~___ CH3 - O - C2H~ \
N - OH N - OH
i~o-CJHT/ CzH~ --(II - 14) (II - 15) HOC2H~ \ HO 3S - C 2 H~\
N - ON N - OH
HOC2H~ / CzHs~~~~~'~~

(II - 16) (II - 17) liOOC - C2H~
N - OH H - N N - OH
HOOC- C2H~

(II - 18) (II - 19) A A
HO- CH2CH2 - N~ N - OH O~ N - OH

(II - 20) (II - 21) A CH~

~ CH30C2H~ /

(II - 22) (II - 23) CH30C2H~ \ HO3SC2H~ \
N - OH N - OH
CH~OC2H~ / HO3SC2H~ /

3~6f~9.~;

(II - 24) (II - 25) C2HsOC2H4 \ HO3SC3H~4 \
N - OH N - OH
C2HsOC2H4 / HO~SC~H~ /

(II - 26) NH2C3Hs \
N - OH
NH2C3Hs /
(II ~ 27) HO-CHz-NH-OH
(II - 28) CH3-O-C2H4-NH-OH
(II - 29) HO-C2H4-NH-OH
(II - 30) HOOC-C2H4-NU-OH
(II - 31) HO3S-C2H~-NH-OH
(II - 32) N2H~C3Hs~NH~OH
(II - 33) CH3-O-C2H4-NH-OH

The hydroxylamine derivative of the present invention can be used in the form of acid salt such as hydrochloride, sul-fate, p-toluenesulfate, oxalate, phosphate, acetate and so forth.
The hydroxyl amine derivative or an acid salt thereof is used at an amount of 0.5 to 50 g, preferably 1 to 20 g, based on one liter of the color developer. In addition, although the above described hydroxylamine derivative can be used together with hydroxylamine salts as far as the effects of the present invention are not spoiled, the latter is added at a ratio of about 1 g or less, preferably 0.5 g or less, based on 1 liter ~3(~

of the color developer (calculated as NH20H l/2H2S04).
In addition, when the hydroxylamine derivative is incorpo-rated in the photo-sensitive material and the color developer is supplied with it by continuously processing the photo-sensitive material, the hydroxylamine is used at a ratio of 0.05 to 5 g, preferably 0.1 to 2 g, per 1 m2 of the photo-sensitive material.
Nextly, nitrogen-containing heterocyclic mercapto com-pounds are described.
Heterocyclic rings in the nitrogen-containing heterocyclic mercapto compounds used in the present invention are preferably selected from a group consisting of an imidazoline ring, an imidazol ring, an imidazolone ring, a pyrazoline ring, a pyrazol ring, a pyrazolone ring, an oxazoline ring, an oxazole ring, an oxazolone ring, a thiazoline ring, a thiazol ring, a thiazolone ring, a selenazoline ring, a selenazole ring, a selenazolone ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a benzimidazole ring, a benztriazole ring, an indazole ring, a benzoxaxole ring, a benzthiazole ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, an oxazine ring, a thiazine ring, a tetrazing ring, a chinazoline ring, a phtharazine ring and polyazaindene rings (for example a triazaindene ring, a tetrazaindene ring, a pentazaindene ring and the like).
Of the above described nitrogen-containing heterocyclic 13C~ S

- 2~ -mercapto compounds, mercapto oxadiazole, mercapto thiadiazole, mercapto triazole expressed by the following general formula [III] and mercapto tetrazole are preferably used:
~III]
(Y)n X I S H

N--N

wherein X is selected from a group consisting of a hydrogen agom, an amino group, a hydroxyl group, a hydrazino group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a -NHCOR1 group, a -NHSO2Rl group or a -R2S group; Y is selected from a group consisting of hydrogen atom, an amino group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a -CONHR9 group, a -COR4 group, a -NHCORs group or a -NHS02Rs group; Z is nitrogen atom, sulfur atom or oxygen atom; n is l when Z is nitrogen atom and O when Z is oxygen atom or sulfur atom; and R1, R2, R3, R4 and Rs are independent-ly selected from a group consisting of an alkyl group, an alkenyl group, a cycloalkyl group and an aryl group.
In more detail describing the general formula [III], the alkyl group expressed by X and Y is preferably selected from those containing 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and a benzyl group. Cycloalkyl group is preferably selected ~3~ S

from a cyclohexyl group, a cyclopentyl group and the like. In addition, the alkenyl group is preferably selected from those containing 2 to 18 atoms such as an allyl group and an octenyl group. Aryl group is selected, for example, from a phenyl group, a naphthyl group and the like.
Furthermore, the alkyl group expressed by R1, R2, R3, R4 and Rs may preferably be linear or branched alkyl groups con-taining 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group. The cycloalkyl group is preferably selected for example, from a cyclopentyl group, a cyclohexyl group and the like. The alkenyl group is preferably selected from those containing 2 to 18 carbon atoms such as an allyl group, an octenyl group and an octadecenyl group. The aryl groups are a phenyl group, a naphthyl group and the like.
Besides, alkyl groups, cycloalkyl groups, alkenyl groups and aryl groups expressed by said X, Y, Rl, R2, R3, R4 and Rs may have a substituent. Such substituent includes an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a halogen atom, nitro group, cyano group, mercapto group, an amino group, a carboxyl group, a hydroxyl group and the like.
The compounds expressed by the general formula [III] ac-cording to the present invention show the following isomeriza-tion. The present invention includes also these isomers.

l~Cr6~

( I )n ( Y )n X~z~S H ~ ~ S

1~ N N--N H

Concrete examples of the compounds expressed by the gen-eral formula [III] will be below described but they are not restrictive.
(General formulae III-1 to III-60) m-l m-2 I ~S H C H 3~N~S H
N N N N

m-3 m-4 CzHs CH2--CH=CH2 CH3~N~S H ~N~S H
N N N N

m-s ' m-6 N H 2 1~1 H O N S H
N--N
N N
m-7 m-s CH3 CzHs N~,S H
N N N N

~3~
-26a-m-s m-l o CH,~HN~SH CH,~N~SH

N N N N
m-ll m-12 N~N~S E~

m-13 m-14 C~H,~(n) CgHI9 C2HsCONH~N~SH CH~ ~ SO2NH~I~SH

N-N N N

m-15 m-16 NHCOCH, NHCOCH~
~ I~SH CH,~N~SH

m-17 ~ m-18 co h~ NHCOC2Hs C2H ~N SH ~ C2Hs~N~SH
N-N
.
A`

la-~6s~s - 26b -m-l g m-so ~NC O

m-2 1 m-2 2 NHCOC3H,(n) NHC
C2Hs~N~S H C~H~N~S H
N N N N

m-2 3 N H S 0 2 ~C H 3 C2Hs~N~S H
N--N
m-2 4 C H
C H 3 C O N H~N ~,S H

N N

~3~ 5 m _ ~- F
~3 ~ C O N H~, N ~,S H

m-2 6 C H zC H 2 ~ C H
CQCH2CH2CONH~N~,S H
N N
m-2 7 CQ

C2HsCONH N SH
~. ~

m-2 8 ~3 N H~, N ~,S H

- 26d -m-2 9 C H ~ 0~ 3 C O N H~ I ~,S H

m-3 o ~3 C2Hs--S~CONH~N~,SH
m-3 1 CH~S 02N ~N S H

m-3 2 [~

CH'~N SH

~, . . ' . - , - '--_', - 26e - -m-3 3 C H 2 C H z S C H 2 C H
CHs~CONH N SH
1`1--N
m-3 4 C2Hs (~CH2NH~ SH

m-3 5 ~3-m-3 6 C2Hs m-3 7 C H ~
CH2=CHCONH N SH

13~6~395 -- 26f --m-3 8 ~C H 2 C O N H ~S H

m-3 9 C H 2--C H = C H 2 ~3CONH~6~ 1 ~,S H
CO O H
m-40 CO~
~ C O N H~ N ~,S H

:
m-4 1 CH~CONH S SH

m - 4 2 (~3 N H~ S ~,S H

13~
~,, -- 26g --m-4 3 C~C H 2C O N H~S~S H
N--IY
m - 4 4 N 02~CONH~S~,S H

m-4s CH2= CHCON H~S~ç~S H

m - 4 6 CH,S 02NH~,S~,S H

.

~ S 0 2 N 11~ S ~,S 11 m-4s C H ~S O 2 N ~ S ~,S H

l~Ctt~
- 26h -m-4 9 C ~ S 0 2 N H~, S ~,S H

m-s o CH3NH~S S H

m-s 1 C2HsN H~,S~S H

m-5 2 CH2=CH--CH2--NH S S H

m~5 3 C2HsOCOCH2--S S SH

m-5 4 ~ ~ .

1~ '', .. . . . . . _ __ . _ . . .. .. .. _ _ _ .

3 r~
J

-- 26i --m-5 5 HOCHzCH2S~s~S H

m-5 6 C"H 23~0~S H

m-5 7 CH3~,o~,S H

m-5 8 H O O C C H 2 S~ O ~,S H

m-s 9 C2Hs o S H

m-6 o H21`r S SH

.~ .

13068r3~ii - 26j -Said compounds have been generally ~nown and disclosed infor example Japanese Patent Unexamined Publication No. 107129/
1976, Japanese Patent Unexamined Publication No. 102621/1973, Japanese Patent Unexamined Publication No. 59463/1980, Japanese Patent Unexamined Publication No. 124333/1984 and BP 1,204,623.
Further, the following heterocyclic mercapto compounds can also be mentioned as preferable examples of the present inven-tion.

N N ~N~S H

N H2 N S H /--\ H
C~ NH~,N~S H
N N \~/11 11 H~3 HXC~H~

IV - 5 IV. - 6 `N~ ~ X

H _~_ C O N H ~N~, S H

C~N~ H O O C~N~

~f~

J~ S ~ [~ N

,~ ~ S N a ~3~ S~ S H
NaO3S N N
IV - 14 N~ ¦ IV - 15 ~N--N

SH SH
IV - 16 N=N IV - 17 ~N=N

SH SH

~CONH~N ¦ CH3CONH~N 7 SH SH

~_ /N 7 ~_N~N_7 ~=N ~=N
SH SH

~ 689~

The above-mentioned exemplified compounds cna be synthe-sized in the light of, for example, J. Chem. Soc. [49], 1748 (1927); J. Org. Chem. [39], 2469(1965); Japanese Patent Un-examined Publication Nos. 89034/1975, 79436/1980, 102639/1976, 594635/1980; Ann. Chem. 44-3, 1954; Japanese Patent Publication No. 28496/1965; Chem. Ber. [20], 231(1887); USP 3,259,976;
Chemical and Pharmaceutical Bulletin (Tokyo) [26], 314(1978);
Berichet der ~eutsche,n Chemischen Gesellsdraft [82], 121(1948);
USP 2,843,491; USP 3,017,270; British Patent 940,169 and Journal of American Chemical Society [44], 1502-1510.
It is specially noted that the use of the above-mentioned heterocyclic mercapto compound in a photo-sensitive material comprising a photo-sensitive silver halide emulsion containing silver halide grains which consist essentially of silver chlo-ride in combination with the sensitizing dye of formula [I] has an advantage that occurrence of fog can be restrained effec-tively even in the case where the possibility of contamination of a bleach-fixing solution with a color developer solution carried in from a previous step is increased and the pH value thereof tends to increase when a photo-sensitive material un-dergoes bleach-fixing process immediately after color develop-ment process.
Among those exemplified hereinabove, the use of mercapto terazole compounds such as (IV-14) thru (IV-21) are especially preferable.

13(~6~395 These nitrogen-containing heterocyclic mercapto compounds may be added to either the color developer or the sensitive material but lt is preferable to add them to the sensitive material. ln the event that they are added to the color devel-oper, they are added at a ratio of 10-6 to 10-4 mol based on 1 liter of the color developer.
The nitrogen-containing heterocyclic mercapto compounds according to the pres,ent invention can be added to a sensitive silver halide emulsion layer or a non-sensitive constituent layer of photogrpahy but it is preferable to add the nitrogen-containing heterocyclic compound to the sensitive silver halide emulsion layer.
Two or more kinds of nitrogen-containing heterocyclic mercapto compound according to the present invention may be added and the nitrogen-containing heterocyclic mercapto com-pounds according to the present invention may be added to two or more different layers. These nitrogen-containing hetero-cyclic mercapto compounds are used at a ratio of 10-~ to 10- 4 mol/m2, preferably 10 7 to 10 5 mol/m2.
Furthermore, the nitrogen-containing heterocyclic mercapto compounds according to the present invention may be added in the form of alkaline metal salts such as a sodium salt, a potassium salt and a lithium salt.
The fog-preventing effect by the combination of said sen-sitizing dye expressed by the general formula [I] with said ~3~

nitrogen-containing heterocyclic mercapto compounds in a method of forming a dye image according to the present invention can reduce not only fog of a silver halide emulsion layer contain-ing silver halide particles spectrally sensitized with said sensitizing dye but also that of other silver halide emulsion layers. This cannot be easily anticipated from the prior art.
The silver halide particles used in the present invention are formed of silver chloride, silver bromide, silver iodide, silver chloro-bromide, silver iodo-bromide, silver chloro-iodide and the like, preferably silver chloro-bromide, and in particular preferably silver chloro-bromide containing silver chloride at a ratio of 10% or more by mol.
An average particle diameter of said single dispersive silver halide particles are not especially limited but it should be l.0 ~m or less, preferably 0.8 ~m or less.
In addition, the silver halide particles used in the pre-sent invention may have regular shapes, such as cubic shape and octahedral shape, and irregular shapes such as sharp shapes.
The silver halide emulsion of the sensitive silver halide emulsion layer according to the present invention may be doped with platinum, palladium, iridium, rhodium, ruthenium, bismuth, cadmium, copper or the like.
Furthermore, this silver halide emulsion can be chemically sensitized. Concretely speaking, it can be sensitized by sul-fur sensitizing agents, such as allylthiocarbamides, N, N-13(~ S

diphenyl thiourea, sodium thiosulfate and cystine, noble metal sensitizing agents, such as gold compounds, palladium com-pounds, platinum compounds, ruthenium compounds, rhodium com-pounds and iridium compounds, or the combinations thereof.
Also, it can be sensitized by reducing agents such as stannous chloride.
The binder used in the constituent layer of the silver halide photo-sensitive material according to the present inven-tion is most generally formed of gelatine such as alkali-treated gelatine or acid-treated gelatine. Also, a part of this gelatine can be used together with gelatine derivatives, such as phthalized gelatine and phenylcarbamoylgelatine, albumin, agar-agar, Arabian rubber, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed poly-vinyl acetate, polyacrylamide, polyvinylalcohol, polyvinyl-pyrolidone and copolymers of these vinyl compounds.
The silver halide photo-sensitive material according to the present invention is subjected to the color developing process after the imagewise exposure to form the dye image.
Particularly useful color developing agents used in the color developer include N, N-diethyl-p-phenylene diamine hydrochlo-ride, N-methyl-p-phenylene diamine hydrochloride, N, N-dimethyl-o-phenylene diamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-~-methane sulfonamide ethyl-3-methyl-4-aminoanilin sulfate, N-ethyl-N-~-hydroxylethyl-13~1~i895 aminoanilin sulfate, 4-amino-3-methyl-N, N-diethylaniline hydrochloride, N-ethyl-N-~-hydroxylethyl-3-methyl-4-aminoani-line sulfate, N-ethyl-N-methoxyethyl-3-methyl-4-aniline-p-toluene sulfonate and the like.
These color developing agents can be used singly or in the form of mixtures of two or more kinds thereof. In addition, the concentration of the color developing agents can be suit-ably selected within a range of 0.01 to 0.05 mol based on 1 liter of the color developer.
The color developer according to the present invention can comprise various kinds of additive for use in the development of photogrpahy in addition to said color developing agent and said hydroxylamine derivative as the preservative. For exam-ple, alkali agents such as sodium hydroxide, potassium hydro-xide, sodium carbonate, potassium carbonate, sodium meta-borate and tertiary potassium phosfate, pH-buffer agents such as sodium hydrogen phosfate, potassium bihydrogen phosfate, biso-dium hydrogen phosfate and potassium bicarbonate, organic sol-vents such as methanol and ethylene glycol triethanol amine and the like can be suitable selected and used. It is preferable that benzyl alcohol as the coloring capacity-improving agent is not contained in the color developer according to the present invention. However, it can be contained in a slight amount.
Benzyl alcohol is contained in the color developer at a ratio of O to S ml, preferably O to 3 ml, per 1 liter of the 13(~6t3~

color developer.
It is particularly preferable in view of an increase of the preservative capacity of the color developer that the color developer according to the present invention comprises a small amount of sulfites, such as sodium sulfite and potassium sul-fite, in combination in addition to said hydroxylamine deriva-tive. The sulfites are used at a ratio of 0.05 to 2 g, prefer-ably 0.1 to 0.3 g, per 1 liter of the color developer.
The color developer according to the present invention can comprise known development-inhibitors. Such development-inhibitors include bromides, such as sodium bromide and potas-sium bromide, chlorides, such as potassium chloride and sodium chloride, and organic development-inhibitors, such as benztria-zole and benzimidazole.
The effects of the present invention is remarkable in the case where the concentration of the color developer according to the present invention is aobut 0.005 mol or more. In parti-cular, in the case where the concentration of the color devel-oper is 0.01 mol or more, the effect of the present invention, that is to say the effect of inhibiting the generation of fog due to the speedy processing in the event that hydroxylamine derivative is used, is remarkably increased. Here, the speedy processing means a processing in which the color development processing time is 90 seconds or less. The temperature of the color developer is set at 20 to 50C, preferably 30 to 40DC.

~3C~68''~

In the speedy processing method according to the present invention it is required to remove an undeveloped silver halide and a developed image silver by the bleach-fixing process after the formation of the coloring matter image by the color devel-opment.
The bleach-fixing time is set at 90 seconds or less, pre-ferably 60 seconds or less.
The bleach used in the bleach-fixing solution includes metal complexes of organic acids in which metallic ions, such as iron ions, cobalt ions and copper ions, are coordinated in organic acids such as polycarboxylic acids, polyaminocarboxylic acids, oxalic acid and citric acid. The most preferable organ-ic acids of said organic acids are polycarboxylic acids and polyaminocarboxylic acids. These polycarboxylic acids may be used also in the form of alkali metal salt, ammonium salt or water soluble amine salt. Concrete examples of these include the following compounds:
(1) ethylene diamine tetraacetic acid (2) diethylene triamine pentaacetic acid (3) ethylenediamine-N-(~-oxyethyl)-N, N', N'-triacetic acid (4) propylene diamine tetraacetic acid (5) nitrilotriacetic acid (6) cyclohexane diamine tetraacetic acid (7) iminodiacetic acid (8) dihydroxyethylglycin citric acid (or tartaric acid) l3a6s~

(9) ethyletherdiamine tetraacetic acid (10) glycoletherdiamine tetraacetic acid (11) ethylene diamine tetrapropvonic acid (12) phenylene diamine tetraacetic acid (13) ethylene diamine tetraacetic acid disodium salt (14) ethylene diamine tetraacetic acid tetra (trimethylammo-nium) salt (15) ethylene diamine tetraacetic acid tetrasodium salt (16) diethylene triamine pentaacetic acid pentasodium salt (17) ethylenediamine-N-(~-oxyethyl)-N, N', N'-triacetic acid sodium salt (18) propylene diamine tetraacetic acid sodium salt (19) nitriloacetic acid sodium salt (20) cyclohexane diamine tetraacetic acid sodium salt These bleaches are used at a ratio of 5 to 450 g/liter, preferably 20 to 250 g/liter.
The bleach-fixing solution may comprise sulfites as pre-servatives in addition to said bleaches if necessary. In addi-tion, the bleach-fixing solution may comprise an ethylene dia-mine tetraacetic acid iron (III) complex salt bleach and halides such as ammonium bromide.
Said halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like in addi-tion to ammonium bromide.

l~a6~s The silver halide-fixing agents used in the bleach-fixing solution include compounds, which react upon silver halide to form water soluble complex salts, used in the usual fixing process, typically thiosulfates, such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates, such as potassium thiocyanate, sodium thiocyanate and ammonium thio-cyanate, thiourea, thioether and the like. These fixing agents are used at a ratio of 5 g/liter or more but in a quantity within a range in which they can be dissolved, in general at a ratio of 25 to 250 g/liter.
In addition, the bleach-fixing solution can comprise vari-ous kinds of pH-buffer agent, such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, singly or in com-bination. Furthermore, the bleach-fixing solution can comprise verious kinds of fluorescent whitening agent, anti-foamant or surfactant. Besides, the bleach-fixing solution can bisulfite-addition products of hydroxylamine, hydrazine and aldehyde com-pounds, preservatives such as N, N-dialkyl-hydroxylamine, organic chelating agents such as polyaminocarboxylic acids, stabilizers such as nitroalcohol and nitrates, organic solvents such as methanol, dimethylsulfoamide and dimethylsulfoxide and the like according to circumstances.
The bleach-fixing solution can comprise various kinds of 13~J6~ 5 bleach-accelerator disclosed in Japanese Patent Unexamined Publication No. 280/1971, Japanese Patent Examined Publication No. 8506/1970, Japanese Patent Examined Publication No. 556/
1971, Belgian Patent 770,910, Japanese Patent Examined Publica-tion No. 8836/1970, Japanese Patent Examined Publication No.
9854/1978, Japanese Patent Unexamined Publ cation No. 71634/
1979, Japanese Patent Unexamined Publication No. 42349/1974 and the like.
The pH of the bleach-fixing solution is set at 5.0 to 9.0, preferably 5.5 to 8.5.
Various kinds of process, such as color development and bleach-fixation (or bleaching and fixation), and furthermore washing, stabilization and drying carried out in case of need, of the silver halide color photo-sensitive material according to the present invention are carried out at temperatures of 25C or more, preferably 30C or more, in view of the speed-up of the processes.
The silver halide photo-sensitive material according to the present invention may be subjected to washing-substitute stabilizing treatments disclosed in Japanese Patent Unexamined Publication No. 14834/1983, Japanese Patent Unexamined Publica-tion No. 105145/1983, Japanese Patent Unexamined Publication No. 134634/1983, Japanese Pate~nt Unexamined Publication No.
18631/1983, Japanese Patent Publication No. 126533/1984, published on July 2, 1984, Japanese Patent Publication No. 233651/1985 published on November 20, 1985 and the like.

, .

13~9~

The preferred embodiments of the present invention are be-low described but they are not restrictive.

The following layers were coated in turn on a titanium dioxide-contained polyethylene side of a support member ob-tained by laminating polyethylene on one side of a paper sup-port member of 170 g/m2 and laminating polyethylene containing anatase type titanium dioxide a a ratio of 11% by weight on the other side of hte paper support member to form silver halide color photo-sensitive materials No. 1 to 25.
The addition quantity was expressed in a quantity per 1 m2 so far as it was not specially mentioned otherwise.
The layer 1 - - - comprising 1.9 g of gelatin, 0.39 g of (based on silver) blue light-sensitive silver chloro-bromide emulsion (Note-1), 1.2 x 10 mol of a yellow coupler expressed by Y-1, the following photo-stabilizer STB-1 of 0.3 g, 0.05 g of the following color contamination-inhibitor (HQ-1), 0.50 g of di-(2-ethylhexyl) phthalate (hereinafter referred to as DOP) and mercapto compounds as shown in Table 1 (0.08 g/m2).
The layer 2 - - - an intermediate layer comprising 0.7 g of gelatine, 15 mg of an irradiation-inhibiting dye (AI-1) and 0.05 g of DOP, in which 10 mg of (AI-2) and 0.05 g of said color contamination-inhibitor HQ-1 are dissolved.
The layer 3 - - - comprising 1.25 g of gelatine, 0.22 g of green light-sensitive silver chloro-bromide emulsion (contain-~t6~

lng silver chloride at a ratio of 70~ by mol), 0.30 g of DOP, in which 0.45 g of the following magenta coupler (M-1) is dis-solved, and 0.02 g of HQ-1.
The layer 4 - - - comprising 1.2 g of gelatine, 0.08 g of HQ-11 and 0.35 g of DOP, in which 0.5 of ultraviolet absorbent (UV-1) is dissolved.
The layer 5 - - - comprising 1.4 g of gelatine, 0.20 g of red light-sensitive silver chloride emulsion, 0.20 g of DOP, in which 0.45 g of the following cyan coupler (C-1) is dissolved, and 0.02 g of HQ-1.
The layer 6 - - - comprising 1.0 g of gelatine and 0.20 g of DOP, in which 0.30 g of UV-1 is dissolved.
The layer 7 - - - comprising 0.5 g of gelatine.
In addition, 0.4 g of 2, 4-dichloro-6-hydroxy-s-triazine sodium as the film-setting agent was added to said layer 4 and said layer 7, respectively, immediately before the application thereof.
(Note 1) Blue light-sensitive silver chloro-bromide emulsion.
Silver chloro-bromie emulsion containing silver chloride at a ratio of 90~ by mol was chemically ripened until the opti-mum sensitivity point to sodium thiosulfate and then spectrally sensitized by the use of sensitizing dyes as shown in Table 1 (at a ratio of 5 x 10-3 mol per 1 mol of silver halide).
Formulae (Y-1) to UV-1 13(,! ~ t~

Each of said sensitive materials No. 1 to No. 25 was ex-posed to a white light through an optical wedge and then sub-jected to the following processes:
(Process) - (A? _ (B), (C) Color development 38C, 3 min 35C, 1 min Bleach-fixation 34~C, 1 min 35C, 1 min Washing . 30 to 35C, 2 min 30 to 35C, 1 min The compositions of the color developer and the bleach-fixing solution are as follows:
[Composition of the color developer]
[A] [B], [C]
Pure water 800 ml 800 ml Ethylene glycol 15 ml Benzyl alcohol 15 ml Preservative*l) 2 g 2 g Potassium bromide 1.2 g Sodium chloride 0.3 g 2.0 g Potassium sulfite 2.0 g 0.1 g Color developing agent 4.5 g 5 g Potassium carbonate 25 g 25 g Nitrilotrimethylene sulfonic acid 2 g 2 g After adding pure water to 1 liter pH 10.1 10.2 is adjusted *l) Preservatives 13~q'~

A, B Sulfuric acid hydroxylamine 1/2 sulfate (HAS) C N, N-diethylhydroxylamine (HA) [Composition of the bleach-fixing solution]
Pure water 600 ml Ethylene diamine tetraacetic acid ion (III) ammonium 65 g Ethylene diamine tetraacetic disodium salt 5 g Ammonium thiosulfate 85 g Sodium hydrogen s~lfite 10 g Sodium metabisulfite 2 g Ethylene diamine tetraacetic acid sodium 20 g Sodium chloride 10 g Color developer 200 ml After adding pure water to 1 liter pH is adjusted to 7.0 with diluted sulfuric acid.
The reflective concentration of a blue monochromatic light was measured for each of the resulting samples. The sensitivi-ty was measured from the characteristic curve [B] corresponding to the yellow dyer image. The gradation and fog were measured.
As regards fog, it was also measured by the use of green mono-chromatic light.
The obtained results are shown in Table 1.

13(;P61~

_ _ _ _ oo-~oOooOoooooooooooOoo ~ ooooooooooooooooooooooooo ,1 ~ o ~n ~ o ,~ r N
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_ _ ,~' ~ m ~ ~ O a~ V) O O `D O r O~ O~ Oo~ r _ C _ U~
ooooooooooooooooooooooooo ~ ooooooooooooooooooooooooo r,, O O r O O O O O rl O r~ rO O O O rO ~0 0 0 0 Vo~ do~ O O O
m o o o o o o o o o o o o o o o o o o o o o o o o o _~ m ~1 m ~ N ~ r1 ~ a~ N ~ N ~0 ~ N Ul rl ~ N r g ~- ~ l ~ ~ - l l ~
V Q N r ` ~ O ~ co rNo O ~ ~ rn ~ ~ ~D ~

_ _ ,_ o wO ~0 0 0 ~oD uo. o ~oD Uol o wO O O O ~00 0 0 0 0 0 0 0 0 0 oD` ~ OOOOOOOOOOOOOOOOOOOOOOOOO
m o o o o O O O O O O .r ~ rl o o o o ~ o o ~ ~r O
~1 O _ O O O O O O O O O O OO O O O O O O O O O O O O O N
V ~r .n ~r ~ v) r~ ù ~
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E- ~ ~
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8 ~ ~ ~ ~ ~ ~ ~ ~ H ~ ~ 1 ( ~ ~ ) ___________.__.__~____\~Y
O ~ N (''I ~r ~ m m o ~ N ~ ~ m m o ,~ N ~ ~r m ¦ 1 ~ rl rl ~1 _i ~1 ~I rl ~I r I N N N N N N

13C~6~

The sensitivity was expressed by a relative sensitivity with the sensitivity obtained in the event that the sensitive mate-rial 1 was processed in accordance with the process [A] as 100.
In addition, the gradation is expressed by an inclination of the characteristic curve having a reflective density of 0.5 to 1.5.
It is found from the results shown in Table 1 that with the color developer [B] using hydroxylamine as the preserva-tive, the color density is reduced, the sensitivity being re-duced and the gradation being softened regardless of the kind of sensitizing dyes and the existence of heterocyclic mercapto compounds, and on the contrary, with the color developer [C]
using N, N-diethylhydroxylamine as the preservative, the sensi-tivity is reduced and the softening of the gradation are not observed but the fog is increased.
It is found that both samples which do not contain a sen-sitizing dye (No. 1 to No. 5) and the samples containing the emulsion sensitized by the comparative sensitizing dye-l (No. 6 to No. 10) exhibit an only slight effect of preventing fog by the heterocyclic mercapto compounds while the samples (No. 11 to No. 25) containing the emulsion sensitized by the sensitiz-ing dyes [I]-7, [I]-ll and [I]-26, in particular containing the heterocyclic mercapto compounds [III]-24, [III]-40 and [III]-46 exhibit a remarkable effect of preventing fog, and furthermore, effectively prevent not only the yellow fog generated in the 13~J~S

blue light-sensitive layer but also the magenta fog generated in the green light-sensitive layer.

The processes were carried out in the same manner as in EXAMPLE 1 excepting that the spectral sensitizing dyes used for the blue light-sensitive silver chloro-bromide emulsion used in the layer 1 were changed as shown in Table 2 (5 x 10- 3 mol per l mol of silver halide and mercapt compounds were added to the layer 1 and the layer 3 as shown in Table 2.
The obtained samples No. 26 to No. 38 were processed in the same manner as in EXAMPLE 1 with the results as shown in Table 2.
Table 2 shows the results obtained in the cases where the samples obtained by adding the mercapto compound [III]-24, which exhibited the best effect of preventing fog in EXAMPLE 1, to the layers containing the blue light-sensitive silver chloro-bromide emulsion sensitized by the comparative sensitiz-ing dye and the sensitizing dyes [I]-3, [I]-7 and [I]-21 and the samples obtained by adding said mercapto compound [III]-19 to the layers containing the green light-sensitive emulsion were processed with the color developers [A], [B] and [C] used in EXAMPLE 1. It is found from Table 2 that the former samples exhibit a great effect of preventing fog by using the sensitiz-ing dye [I] together with the heterocyclic mercapto compounds [III] when processed with the color developer [C] in the same ~3~6~ 5 manner as in EXAMPLE 1 and furthermore a remarkable effect of preventing hte yellow fog in the case whre the heterocyclic mercapto compounds are added to -the layer 3 which is the green light-sensitive emulsion layer.
In addition, it is found that also the samples obtained by dividedly adding the heterocyclic mercapto compounds to the layer 1 and the layer 3 (the blue light-sensitive layer and the green light-sensitive layer) exhibit a great effect of prevent-ing yellow fog and magenta fog when processed with the color developer [C].

The samples No. 26, No. 27, No. 35 and No. 36 used in EXAMPLE 2 were subjected to the imagewise exposure and then processed in the same manner as in the processes [B], [C].
However, in this EXAMPLE the pH of the color developers [B], [C] used in the processes [B], [C] was changed to 9.7, 10.1 and 10.5, respectively. The harmony (the inclination at the reflective concentration of 0.5 to 1.5) was determined from the characteristic curves obtianed by the measurement of the reflective concentration of the obtained samples by the use of a blue monochromatic light. The results are shown in Table 3.
It is found from the results shown in Table 3 that the samples sensitized by the comparative sensitizing dye exhibit considerable changes in the gradation with the change of the color developer in pH due to the addition of the heterocyclic 13~

mercapto compounds. The fluctuating range of harmony has a tendency of increasing in the case [C] where N, N-diethylhydro-xylamine is used as the preservative of the color developer.
On the contrary, the sample No. 36 according to the present in-vention exhibits a slight fluctuation in the gradation with a change of pH.

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~3(~ J, On the reflective support used in EXAMoeLE 1 following layers were provided in order from the support to prepare silver halide color photo-sensitive materials No. 39 to 62.
Layer 1 - - - A layer comprising 1.4g of gelatin, 0.3g of blue light-sensitive silver chloro-bromide emulsion(Note 2), 1.1 x 10- 3 mol of yellow coupler(Y-2), 0.3g of STB-1, 0.05g of HQ-1 and 0.5g of di-nonylphthalate of in which 0,.1g of N,N-diethyl-(2,5-di-t-amylphenoxy) acetamide is dissoived.
Layer 2 - - - Same as Layer 2 of EXAMPLE 1.
Layer 3 - - - A layer comprising 1.25g of gelatin, 0.3g of green light-sensitive silver chloro-bromide emulsion(Note 3), 0 4g of magenta coupler(M-1) dissolved in 0.3g of DOP, 0.2g of STB-2, 0.1g of STB-3, and 0.02g of HQ-1.
Layer 4 - - - Same as Layer 4 of EXAMPLE 1.
Layer 5 - - - A layer comprising 1.4g of gelatin, 0.20g of red light-sensitive silver chloro-bromide emulsion (Note 4), 0.45g of cyan coupler(C-1) dissolved in 0.2g of DOP, 0.10g of STB-1 and 0.025g of HQ-1 and 0.5g of di-nonylphthalate of in which 0.1g of N,N-diethyl-(2,5-di-t-amylphenoxy)acetamide is dissolved.
Layer 6 - - - Same as Layer 6 of EXAMPLE 1 Layer 7 - - - Same as Layer 7 of EXAMPLE 1 ~3~ 'q~

(STB-2) C8 17( ) ~C4Hg (t) (t) HgC4/~J
C8Hl7 (n) (STB-3) OH OH
(t) HgC4$~/CH2 ~ C4Hg (t) (Note-2) Blue light-sensitive silver chlorobromide emulsion:
Silver chlorobromide emulsion containing cubic silver chlorobromide crystals, said silver chlorobromide containing silver chloride at a ratio of 99.5 % by mol and having an average grain size of 0.70J~m, was chemically ripened by the use of sodium thiosulfate and potassium choloroaurate to an optimum sensitivity point. Thereafter, 5 x 10- a mol per 1 mol of silver halide of a sensitizing dye given in Table 4 and 2 x 10-~ mol per 1mol of silver halide of the mercapto compound given in Table 4 were added to the emulsion.

(Note-3) Green light-sensitive silver chlorobromide emulsion:
Silver chlorobromide emulsion containing cubic silver chlorobromide crystals, said silver chlorobromide containing silver chloride at a ratio of 99.1 % by mol and having an average grain size of 0.40~ m, was chemically ripened by the 13C~8~5 use of sodium thiosulfate and potassium choloroaurate to an optimum sensitivity point. Thereafter, 3 x 10- 3 mol per 1 mol of silver halide of a sensitizing dye (GSD-1) given hereinbelow and 2.5 x 10- 4 mol per lmol of silver halide of the mercapto compound given in Table 4 were added to the emulsion.

(Note-4) Red light-sensitive silver chlorobromide emulsion:
Silver chlorob,romide emulsion containing cubic silver chlorobromide crystals, said silver chlorobromide containing silver chloride at a ratio of 99.6 % by mol and having an average grain size of 0.42~ m, was chemically ripened by the use of sodium thiosulfate and potassium choloroaurate to an optimum sensitivity point. Thereafter, 0.8 x 10- 4 mol per 1 mol of silver halide of a sensitizing dye (RSD-1) given hereinbelow and 2.5 x 10-~ mol per 1 mol of silver halide of the mercapto compound given in Table 4 were added to the emulsion.

>=CH-C--CH~

(CH2) 2SO3H (1H2~ 2SO3 2 S ) 3 ~3~

Cl~CH3 ~O ~CH=C~ ,C-CH~< ~

(CH2 ) 3S03 ( 2 ) 3 3 CH3-C-COCHCONI ~
CH3 ¦ NHCOlCHcH2so2cl2H25 0~,~0 CH3 N

The photo-sensitive materials thus obtained were subjected to white exposure through an optical wedge and, thereafter, to the following processes:

(Process) [D], [E], [F] and [G]
Color Development 35DC 45sec.
Bleach-Fixing 35DC 45sec.
Washing 30~ 34C 2min.

The compositions used of the color developera with respect to the processes are as follows:

13~

[Composition]___[Process] _ _ __ _ [D] and [E] [F] and [G]
Pure Water 800ml 800ml Triethanol amine 10g 10g Hydroxylamine sulfate 1.8g N,N-diethylhydroxyl- - 5g amine([~]-3) - 5g Sodium chloride 2.8g 2.8g Potassium sulfite 0.3g 0.3g Color developing agent* 4.5g 4.5g Ethylenediaminetetra-acetic acid 1.0g 1.0g Potassium carbonate 27g 27g Diaminostilbene type fluorescent brightening agent 2g 2g Add water to make the total volume of 1liter and adjust pH
at 10Ø

As bleach-fixing solution the followings were used with reference to the respective processes:
[D] and [F]
The same bleach-fixing solution as used in Example 1 was used except that this solution did not contain color developer and pH was adjusted to 6.2.
[E]
The bleach-fixing solution used for process [D] and the color developer used for [E] were mixed at a ratio of 1:1 and pH thereof was adjusted to 7Ø
[G]

3~3t~ q~j The bleach-fixing solution used for process lD] and the color developer used for [F] were mixed at a ratio of 1:1 and pH thereof was adjusted to 7Ø

The reflective density measurement of the respective samples were corried out and sensitivity, gradation and fog of the respective samples were obtained from the characteristic curves thereof, The results are shown in Table 4. In the table sensivity is expessed in terms, of a relative sensitivity when the sensitivity of Comparative Sample 39 with the process [F] is made 100.

~ 55 ~

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It is apparent .from the results shown in Table 4 that fogcan be restrained effectively in the samples, in which exemplified mercapto compounds m -24, ~ -14 and ~ -20 in combination with a blue dye sensitizer of the present invention are employed (Samples Nos. 48, 49, 50, 54, 55, 56, 60, 61 and 62), in respective cases when they are processed with either [D~,[E], [F] or [G]. In comparison therewith, with respect to those samples, in which either one of sensitizing dye or mercapto compound outside the scope of the invention is used (Samples Nos. 39, 40, 41, 45, 46, 47, 51, 52, 53, 57, 58 and 59), although occurrence of fog is relatively low when these samples were processed with [D], increase in the fog was observed when N,N-diethylhydroxyl-amine was employed as the presevative (in process [F]) and this tendency was further amplified in process [G] due to contamination by color developer.
In accordance with the present invention, occurrence of fog can be effectively restrained even in the process [G] and this effect was found to be remarkable when a mercapto tetrazole compound such as ~ -14 or ~ -20 is employed.

Samples 63 thru 86 were prepared respectively in the same manner as Samples 39 thru 62 in EXAMPLE 4, exept that in the samples of this EXAMPLE a half amount of mercapto compound used in layer 1 of the respective samples in EXAMPL 3 were further added to layer 2.

The samples thus prepared were processed in the same manner as in EXAMPLE 4, with the proviso that, in this EXAMPLE, 10g per 1 liter of color developer of ~ -25 was used in place of -3 as a preserver for the color developer.
The results are shown in Table 5.
It is apparent from the table that similar effect as obtained in EXAMPLE 4 can also be obtainable in the case where ~ -25 is employed as the preserver for the color developer.

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Claims (17)

1. A method of processing light-sensitive silver halide photographic material which comprises processing an imagewise exposed color light-sensitive silver halide photographic material comprising a support and, provided thereon, at least one silver halide emulsion layer containing light-sensitive silver halide grains which are sensitized with a sensitizing dye of general Formula I
I

wherein Z1 and Z2 independently represent a group of atoms necessary to complete a heterocyclic ring consisting of a thiazole, a benzothiazole, a naphthotiazole, a selenazole, a benzoselenazole or a naphthoselenazole, wherein said heterocyclic ring may have a substituent; R1 and R2 are independently selected from a group consisting of alkyl, alkenyl, and aryl; R3 is selected from a group consisting of hydrogen methyl and ethyl; X1 is an anion and 1 is 0 or 1; with a color developer solution containing an aromatic primary amine color developing agent in the presence of at least one hydroxylamine derivative of general Formula II or a water soluble salt thereof II
wherein R21 and R22 are independently an alkyl group having 1 to 4 carbon atoms which may have a substituent; and at least one nitrogen containing heterocyclic III

wherein X is selected from a group consisting of hydrogen amino, hydroxyl, hydrazino, alkyl, alkenyl, cycloalkyl, aryl, -NHCOR1, -NHSO2R1, and -R2S group;
Y is selected from a group consisting of hydrogen, amino, alkyl, alkenyl, cycloalkyl, aryl, -CONHR5, -COR4 group, a -NHCOR5 group or -NHSO2R5 group; z is nitrogen, sulfur or oxygen; n is 1 when Z is nitrogen and 0 when Z is oxygen or sulfur; and R1, R2, R3, R4 and R5 are independently selected from a group consisting of alkyl, alkenyl, cycloalkyl and aryl;
processing for a maximum of 90 seconds with said color developer, and removing developed silver and undeveloped silver halide with a bleaching solution and a fixing solution or with a bleach-fixing solution.

2. The method of claim 1, wherein Z1 and Z2 independently represent a group of atoms necessary to complete a heterocyclic ring selected from a group consisting of a thiazole ring, a benzothiazole ring, a selenazole ring, a benzoselenazole ring and a naphthoselenazole ring, wherein said heterocyclic ring may have a substituent.

3. The method of claim 2, wherein Z1 and Z2 independently represent a group of atoms necessary to complete a heterocyclic ring selected from a group consisting of a thiazole, a benzothiazole, a selenazole and a benzoselenazole, wherein said heterocyclic ring may have a substituent.

4. The method of claim 3, wherein Z1 and Z2 both represent a group of atoms necessary to complete a benzothiazole which may have a substituent.

5. The method of claim 1, wherein R1 and R2 independently represent a substituted or unsubsti-tuted alkyl group having 1 to 6 carbon atoms.

6. The method of claim 5, wherein R1 and R2 independently represent an ethyl group, a propyl group or a butyl group.

7. The method of claim 1, wherein at least one of R1 and R2 represents a carboxyalkyl group or a sulphoalkyl group.

8. The method of claim 5, wherein at least one of R1 and R2 represents a carboxyalkyl group or a sulphoalkyl group.

9. The method of claim 8, wherein R3 is hydrogen, methyl or ethyl.

10. The method of claim 1, wherein R21 and R22 are both ethyl groups.

11. The method of claim 1, wherein said compound represented by formula [II] is selected from a group consisting of a N,N-dimethylhydroxylamine, a N,N-diethylhydroxylamine, a N,N-dipropylhydroxyl-amine, a N,N-dibutylhydroxylamine and water soluble salts of these compounds.

12. The method of claim 1, wherein said nitrogen-containing heterocyclic mercapto compound is present either in said color developer solution or in said light-sensitive silver halide photographic material.

13. The method of claim 12, wherein said nitrogen-containing heterocyclic mercapto compound is present in said light sensitive silver halide photographic material.

14. The method of claim 13, wherein said nitrogen-containing heterocyclic mercapto compound is present in said light-sensitive silver halide photographic material at an amount of 10 8 to 10 10 mol per m2 thereof.

15. The method of claim 13, wherein said nitrogen-containing heterocyclic mercapto compound is present in said light-sensitive silver halide photographic material at an amount of 10-7 to 10-5 mol per m2 thereof.

16. The method of claim 1, wherein said hydroxyl-amine compound is present in said color developer solution and said nitrogen-containing heterocyclic mercapto compound is present in said light-sensitive silver halide photographic material.

17. A method of forming a dye image by the use of a light-sensitive silver halide color photographic material comprising a support and, provided thereon, at least one silver halide emulsion layer containing a dye image forming coupler and light-sensitive silver halide grains which are sensitized with a sensitizing dye of general Formula I

I

wherein Z1 and Z2 independently represent a group of atoms necessary to complete a heterocyclic ring consisting of a thiazole, a benzothiazole, a naphthothiazole, a selenazole, a benzoselenazole or a naphthoselenazole, wherein said heterocyclic ring may have a substituent; R1 and R2 are independently selected from a group consisting of alkyl, alkenyl, and aryl; R3 is selected from a group consisting of hydrogen, methol, and ethyl; X1 is an anion, and 1 is 0 or 1; with a color developer solution containing an aromatic primary amine color developing agent in the presence of at least one hydroxylamine derivative of general Formula II or a water soluble salt thereof;

II
wherein R21 and R22 are independently an alkyl group having 1 to 4 carbon atoms which may have a substituent and at least one nitrogen containing heterocyclic mercapto compound selected from mercaptotetrazole and compounds of Formula III:

III
wherein X is selected from a group consisting of hydrogen amino, hydroxyl, hydrazino, alkyl, alkenyl, cycloalkyl, aryl, -NHCOR1, -NHSO2R1, and -R2S group;
Y is selected from a group consisting of hydrogen, amino, alkyl, alkenyl, cycloalkyl, aryl, -CONHR3, -COR4, a -NHCOR5 and -NHSO2R5; Z is nitrogen, sulfur or oxygen; n is 1 when Z is nitrogen and 0 when Z is oxygen or sulfur; and R1, R2, R3, R4 and R5 are independently selected from a group consisting of alkyl, alkenyl, cycloalkyl and aryl;
processing for a maximum of 90 seconds with said color developer, and removing thereafter developed silver and undeveloped silver halide with a bleaching solution and a fixing solution or with a bleach-fixing solution.