CA1332029C - Method for processing a silver halide color photographic material - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A method for continuously processing an imagewise exposed silver halide color photographic material with a color developer containing at least one aromatic primary amine color developing agent is disclosed, in which said color developer contains at least one compound selected from the group consisting of a compound represented by formula (I):

(I) wherein R1, R2, and R3 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; R4 represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrazino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted amino group; or R3 and R4 are taken together to form a heterocyclic group; X1 represents a divalent group; and n represents 0 or 1, provided that when n is 0, R4 represents an alkyl group, an aryl group, or a heterocyclic group, and a compound represented by formula (II):

Description

;~

A METHOD FOR PROCESSING A SILVER
~ALIDE COLOR PHOTOGRAPHIC MATERIAL

FIELD OF THE INVENTION
This invention relates to a method for processing a silver halide color photographic material. More particularly, it relates to a method for processing a silver halide color photographic material at a markedly reduced replenishment rate of a color developer while preventing, even on continuous processing, a variatîon of photographic characteristics.

. ',:`'"
B~ACKGROUND OF THE INVENTION - ~-In continuous processing of silver halide color photographic materials, reduction o the amount of a replenisher or replenishment rate greatly contributes , toward saving of resources, control of environmental pollution, and reduction of cost. In particular, since a color developer is not only causative of environmental pollution due to its high BOD (biological oxygen demand) and COD (chemical oxygen demand) but also expensive, various studies have been conducted to establish a technique for reducing the amount of the replenisher.
Known techniques so far proposed in this connection include a method of using a photographic emulsion having a high silver chloride content to thereby considerably ~3320~9 ~
:

decrease the amount of an overflow of a color developer as disclosed in JP-A-61-70552 ( the term "JP-A" as used herein means an "unexamined published Japanese patent application"), a method of using a specific coupler and processing the photographic material with a color developer having a high bromide content as disclosed in JP-A~53-146625 and JP-A-59-198454, and a method of using a silver iodobromide emulsion and a specific coupler as , disclosed in JP-A-61-243453, JP-A-61-251851, JP-A-61-251852, and JP-A-61-261741.
However, any of these techniques is still unsatisfactory because a serious variation of photographic characteristics is induced or og ~enerates during continuous processing.
As long as a color developer is replenished in continuous processing at an ordinary rate of from about 180 to 1,000 nu/m2, serious problems may not occur.
However, if the replenishment rate i~ decreased to about 20 ml to 120 ml per m2 as in the present invention, various disadvantages would become conspicuous such that the retension time of the color developer in a tank increases to accelerate deterioration of processing solution components, particularly a preservative (anti-oxidant) and a color developing agent (deteriorated due to oxidation); the processing solution components tend to be i3~2029 concentrated by evaporation; ~he pH of the processing solution is liable to decrease due to absorption of carbonic acid gas; and difficulty in precise control of replenishment results in variation of the composition of the processing solution in the ~ank.
That is, there has not yet been established a technique ~or processing which realizes great reduction of replenishmen~ rate, while satisfying practical demands, without causing variation of photographic characteristics : or undesired fog, even on continuous processing.
On the other hand, magenta couplers represented by formula (III):
~ .
10 ~ X
~: N I Z
Z C '~Z 1~

wherein Rlo represents a hydrogen atom or a substituent; X
represents a hydrogen atom or a group releasable on . coupling reaction with an oxidation product of an aromatic primary amine developing agent; Za~ Zb~ and Zc each represents a methine group, a substituted methine group, =N- or -NH-; one of the Za~zb bond and Zb-zc bond i5 a double bond, with the other being a single bond; when the Zb-zc bond is a carbon-carbon double bond, it may be a ~3~2~29 part of an aromatic ring; the formula (III) includes a dimer or a hisher polymer formed at Rlo or X or at Za~ Zb or Zc representing a substituted methine ~roup, are known to produce an excellent hue as described in JP-A-59-162548, JP-A-60-43659, JP-A-59-171956, JP-A-60-172~82, JP-A-60-33552, and U.S. Patent 3,061,432 and have been studied extensively.
It was proved, however, that the magenta couplers of formula ~III) cause an increase of stains when color development is carried out a~ a low replenishment rate of a color developer. Although there were made several proposals to prevent such stains as disclosed in JP-A-49-11330, JP-A-50-57223, JP-A-56-85747, and JP-B-56-8346 (the term "JP-B" as used herein means an "unexamined published Japanese patent application"), sufficient effects have not ::
yet been attained.

SUMMARY OF THE INVENTION ~-~
~One object of this invention is to provide a method of `~ ~processing at a considerably reduced rate of replenishment of a color developer.
Another object of this invention is to provide a ~;
method of processing which is less causative of a variation of photographic characteristics and of fog even when processing is carried out continuously.

,, . !

It has now been found that the objects of this invention can be accomplished by a process for ~ continuously processing an imagewise exposed silver halide :~ color photographic material with a color developer ~: containing at least one aromatic primary amine color developing agent, in which the color developer contains at -~ ~ least one compound selected from the group consisting of a ~; compound represented by formula (I):

R .

wherein Rl, R2, and R3 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a subi3tituted or unsubætituted heterocyclic group, R4 represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrazino group, a substituted or unsubstituted alkyl glroup, a isubstituted or unsubstituted aryl group, a substituted or unsubstituted heterocylic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubætituted carbamoyl group, or a substituted or unsubstituted amino group or ~3 and R4 are taken together to form a heterocylic group; xl represents a divalent group; and n represents 0 or 1, provided that when n is 0, R4 represents an alkyl group, an aryl group, or a heterocylic group, and a compound represented by formula ~

~ N - R S - N ~ R (II) wherein R5 represents a substituted alkylene group; and R6, R7, R8, and R9, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and the color developer is replenished at a replenishment rate of from 20 to 120 m~ per m2 of the photographic material.
The method according to the present invention is preferably applied to processing of a silver halide color photographic material containing at least one of the above-described magenta couplers represented by formula (III).
In order to ensure the above-described effects of the invention, it is preferable to use a color developer which :'.

does not contain such a component (except for the color developing agent) that would exert great influences on photographic characteristics.
For instance, in case when a color developer is concentrated to have an increased content of bromine or iodine ion, which is usually present in a color developer as an antifoggant, the development rate of a silver halide emulsion is reduced, resulting in reduction of sensltivity or insufficient maximum density. Further, since the iodine ion, even in a small quantity, has an activity to intensify internal latent image, it sometimes causes serious fog. It is preferable accordingly that the color developer contains substantially no bromine or iodine ion.
Further, a sulfite ion, usually added as a preservative for various developing agents, reacts with an oxidation product of a color developing agent, thus becoming a competitor to couplers. The sulfite ion also serves as a solvent for a silver halide emulsion to give influences to the development rate or developability of maximum density and, as a result, causes a variation of photographic characteristics. Since the change of sulfite ion concentration thus results in significant variation of photographic characteristics, it is preferable in the present invention that the color developer contains substantially no sulfite ion.

13~2029 It is furthermore preferred in the present invention that the color developer contains substantially no hydroxylamine not only because hydroxylamine becomes a competitor to couplers similarly to sulfite ion but also decomposition products of the hydroxylamine frequently influence silver developability.

DETAILED DESCRIPTION OF THE INVENTION
The compounds represented by formula (I), i.e., hydrazine analogues derived from hydrazines or hydrazides, are described in detail.
Rl, R2, and R3 each represen~s a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having from 1 to 20 carbon atoms, e.g., methyl, ethyl, sulfopropyl, carboxybutyl, hydroxyethyl, cyclohexyl, benzyl, phenethyl), a substituted or unsubstituted aryl group (preferably having from 6 to 20 carbon atoms, e.g., phenyl, 2,5-dimethoxyphenyl, 4-hydroxyphenyl, 2-carboxyphenyl)t or a substituted or unsubstituted heterocyclic group [preferably a 5- or 6-membered ring containing from 1 to 20 carbon atoms and at least one hetero atom, e.g., oxygen, nitrogen, and sulfur (e.g., pyridin-4-yl, N-acetylpiperidin-4-yl)].
R4 represents a hyd;rogen atom, a hydroxyl group, a substituted or unsubstituted hydrazino group (e.g., hydrazino, methylhydrazino, phenylhydrazino), a substituted or unsubstituted alkyl group (preferably containing from 1 to 20 carbon atoms, e.g., methyl, ethyl, sulfopropyl, carboxybutyl, hydroxyethyl, cyclohexyl, benzyl, ~-butyl, n-octyl), a substituted or unsubstituted aryl group (preferably having from 6 to 20 carbon atoms, e.g., phenyl, 2,5-dimethoxyphenyl, 4-hydroxyphenyl, 2-carboxyphenyl, 4-sulfophenyl), a substituted or uncubstituted heterocyclic group [preferably a 5- or 6-membered ring containing from 1 to 20 carbon atoms and at least one hetero atom selected from oxygen, nitrogen, and sulfur ~e.g., pyridin-4-yl, imidazolyl)], a substituted or unsubstituted alkoxy group (preferably having from 1 to 20 carbon atoms, e.g., methoxy, ethoxy, methoxyethoxy, benzyloxy, cyclohexylo~y, octyloxy), a substituted or unsubstituted aryloxy group (preferably having from 6 to carbon atoms, e.g., phenoxy, p-methoxyphenoxy, p-carboxyphenoxy, p-sulfophenoxy), a substituted or unsubstituted carbamoyl group (preferably having from 1 to carbon atoms, e.g., unsubstituted carbamoyl, N,N~
diethylcarbamoyl, phenylcarbamoyl), sr a substituted or unsubstituted amino group (preferably having up to 20 carbon atoms, e.g., amino, hydroxylamino, methylamino hexylamino, methoxyethylamino, carboxyethylamino, sulfoethylamino, N-pheny].amino, p-sulfophenylamino).

:
13~2029 Substituents for Rl, R2, R3, and R4 preferahly include a halogen atom (chlorine, bromine) and hydroxyl, carboxyl, sulfo, amino, alkoxy, amido, sulfonamido, carbamoyl, sulfamoyl, alkyl, aryl, aryloxy, alkythio, arylthio, nitro, cyano, sulfonyl, and sulfinyl groups, each of which may be further substituted.
Xl preferably represents a divalent organic NH -group, such as -CO-, -S02-, and -C-. n is O or 1. When n is 0, R4 is selec~ed from a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocylic group. Rl and R2, or R3 and R4 may be taken together to form a heterocylic group.
When n is 0, it is preferable that at least one of Rl, R2, R3, and R4 is a substituted or unsubstituted alkyl group, more preferably Rl, R2, R3, and R4 each represents a hydrogen atom or a substituted or unsubstituted alkyl group, provided that all of them do not simultaneously represent a hydrogen atom, and most preferably Rl, R2, and R3 each represents a hydrogen atom, and R4 represents a substituted or unsubstituted alkyl group; Rl and R3 each repre~ents a hydrogen atom and R2 and R4 each represents a substituted or unsubstituted alkyl group; or Rl and R2 each represents a hydrogen atom, and R3 and R4 each . ' ., ` !

represents a substituted or unsubstituted alkyl group, or R3 and R4 are taken together to form a heterocyclic group.
When n is 1, it is preferable that xl represents -CO-, R4 represents a substituted or unsubstituted amino group, and Rl, R2, and R3 each represents a hydrogen atom or a substituted or unsubstituted alkyl ~roup.
n is preferably 0.
The alkyl group as represented by Rl, R2, R3, or R4 preferably contains from 1 to 10 carbon atoms, and more preferably from 1 to 7 carbon atoms. Preferred substituents for the alkyl group include a hydroxyl group, a carboxyl group, a sulfo group, and a phosphono group.
When the alkyl group has two or more substituents, they may be the same or different.
Included in the compounds of formula (I) are dimers, trimers and polymers formed at Rl, R2, R3, or R4.
- Specific examples of the compounds of formula (I) are shown below for illustrative purposes only but not for limitation. ~
1 ~ . ' ' ' ' ~' ;"
~' ..

": ! , 1332029 ::

( I--1 ) ~

~NNHZ

., ( I - 2 ~
C H a N H N H C H

3 ) : --HOC~ H~
/NNHZ

(I 4) N3NHNH~

. ~
. ~ ~
5) :~ ~
~ .
Nllz NEI~NI:INH: ~:

6 ) CN H H

~ ~ ......
~ 12 ~ ~

13~2029 tl--7) ~:
CHz COOH
NHz N

(I-8) H O O C C H z N H N H C H z C O O H

( I--9 ) ~ N~z NH~CH2~NHNH2 :
:~ ~
( I--l 0 ) ` ~ NH2 NHCH2 CHz OH

OH ~

~ .
( I - 1 2 ) NH2 :NH- (CHz)3 ~SOl H ~:`
t I - 1 3 ) NH2 NH- (CHz)4 -S03 H

N H 2 N H - ( C H 2) 3 ~ C O O H

' ~
13 - ~:

13~2029 (I-15) HOOC ~ CH2NHNHCHz ~ COOH

(I-16) CH2~ COONa NHzN
CH2~ COONa :::
(I-17) ~<
S03 Na ~I-18) :~ NaOOCCHNHNHCHCOONa ;

; - tI-l9) NH2NHCHzCH2COONa ;
(I-20) ;
1 ~
NH~NHCX2COONa ~
tI-21) ~:;
H2NNHCHzCH2 S03 Na ' :~ -.' ~ .

~332029 (1-22) C~H~(n~
HzNNHCHCOOH
~I-23) :~ C~ H,3(n) ` I .:' ~.
; HzNNHCHCOOH
24) C4 H9(n) ~ ~
~: H2NN~CHCOOH)z :~
(1-25) HzNN~CH2CHz S03 Na)2 -.
"~
:: (1-26) HzNN~CHzCH2CH2SO3Na)2 -~

27) HzNN~CHCOOH)z (I-28~ ~`

I HzNNHCHCOOH :.

; ~ ~; - , ~ 15 :

(I--2 9) ~.CHz CHz OH

(I--3 0) ;: H~ NNHCH2 CH2 N~

.::
~ I--3 1 ) :~ ~ C :, :: H2 NN~CH2 CH2 N~ ) 2 C H

( I--3 2 ) .
C H 2--N - (~ H 2 C H z~

: ~ i (Average Molecular Weight: ca. 4,000) ~; ~1--3 3) ~: ~CH2--CH 3~ i ~CHz -CH ~ ~
'` ,~ I , ~ 1:` ` ~ C O O H
.
NHNH~
. x : y ~ 6 0 4 0 ~:
(Average Molecular Weights ca. 20,000) .;~
`

' ~

1332~29 (I--3 4) NH2 NHCONHz (I-35) N H
NH2 NHCNHz (1-36) NHz NHCONHNHz ' ~:
(1-37) t I - 3 8 ) NH2 NH S O2 NHNHz ; ~ `:

(I--3 9) CHJ NHNH S O2 NHNH CH3 ~ `~

~ (I--40) :~ NH2 NHCONH-- (CH2)3 -NHCONHNHz ~`

(I--41) ~: NH2 NH S 02 NH~NH S O2 NHNHz ' ~

~':

- 17 - ` .

(1-42) NHzNHCOCONHNHz (I-43) ::

~:~ (I-44) NHCONHNHz ~: (I-453 NHzNHCON NCONHNHz , \ / ::~

(I 46) . .

7) CH~O O
NHCNHNH2 ;~

, (I 48) O
::~ HOOC ~ NHCNHNH2 133~29 :

(I-49) ,~ 11 ,''.
HO3S ~ NHCNHNHz (I-50) HO o -.
: ~ NHCNHNH2 (I-513 ;
O ,~
H2NSOz ~ NHCNHNHz (I-52) HOOC O

HOOC ~

(1-53) ~:
CH3 o -NaO3S ~ NHCNHNH2 ~ f .' .:

,~'' '' '.`'~ '~
, .

- 1 9 - : , .'~, .'.'!

13~2029 ~

( 1--5 4 ) N a 03 S ~NH CNHNH2 ~ , :

, ~N H C N H N H z N H C O N H N H z ;~

t I - 5 6) O O
H z NNH C N H~3N H C N H N H z ~ , ~
: (I-57) O O
~: 11 11 ,' H2 NNHCNH-- (CH2)b --NHCNHNHz ( I 5 8 ) :
CH3~ 11 ~N--CNHNHz (I--5 9) HOOCCHz~ 11 /N--CNHNH2 :
HOOCCHz ( I - 6 0 ) Il ~:
NaO3 SCHz CH2 NHCNHNHz ( I - 6 1 ) HOOCCHz CH2 NHCNHNHz ~;

(1-6 2) ;:.;`:.
O
~CH2 NHCNHNHz ; ~ S~)3 Na . (I-63) ~;~
NHz NHCOOC2 Hs (1-6 4) . . .
~ NHz NHCOCH3 ~

'.".
' '~, ~ `

1332o29 (I -6 5) . NHz NHCo~3 HO

(I-6 63 N H 2 N H S 0 2 ~3C H

~I--6 7) NH2 NHCHz P03 H2 (I--6 8) NHz NHCO~
:: ~ N H z ( I--6 9 ) `~ NHz NHCO~CONHNH2 7 0) C O N H N H 2 ~

~;., tI-71) ;

HOOC ~ CO-NHNHz (1-72) :

. NaO3S ~ CONHNH

: ~I-73) ;~
(CH3)3CCONHNHz . :~ .. .
~ (I-74) :

o ., ~
Il , ~CH3)3COCNHNH2 .
` ~ . , j; ,' (I-75 ~ ~CONHNH.
(I-763 . \N ~CONHNH2 ~:~ H

`;`"

1332o29 (I--7 7) (CH3)z N~3CoNHNH2 (I--7 8) ~CONHNH2 (I--7 9) [~N3~
C ONHNHz `

I - 8 0 ) ~
HOCH2 CH2 S2 NHNH2 ~ .

( I - 8 1 ) Na O3 SCH2 CH2 CONHNH2 (I -8 2) ```
H, NCONHCHt CHI SOz NHNH.

"~

, :;,.' ~' ~

1332~29 ::

(I -8 3) HOOC
~S O 2 N H N H
HOOC

H 2 P 0 3 H z ~ :~
:~ H2 NN~ ~:
CHz P 03 Hz 8 5) Hz NNHCHz CHz POs H2 ; .
( I - 8 6) O H -. .~;
::~ ~CHz NCHz CH~ (n = 20 - 300) ~:
; NHz ~:
:

:::

Additional examples of the compounds of formula (I) are given in Japanese Patent Application No~. 170756/86 (pp 11-24), 171682/86 (pp 12-22), and 173468/86 (pp 9-19) (corresponding to JP-A-63-146041, JP-A-63-146042 and JP-A-63-146043, respectively).
Many of the compounds of formula (I) are available as commercial products. They can also be synthesized by general processes by referring to, e.g., Orqanic SYntheses, Coll. Vol. 2, 208-213, Jour. Amer. Chem. Soc., Vol. 36, 1747 (1914), Yukaqaku, Vol. 24, 31 (1975), Jour.
Ora. Chem., Vol. 25, 44 (1960), Yakuaaku Zasshi, Vol. 91, 1127 (1971), Orqanic SYntheses, Coll. Vol. 1, 450, Shin Jikken Kaaaku Koza, Vol. 14, III, 1621-1628, Maruzen, Beil., Vol. 2, 559, ibid, Vol. 3, 117, E.B. Mohr et al., , Inor~. SYn., Vol. 4, 32 (1953), F.J. Wilson and E.C.
Pickering, J. Chem. Soc., Vol. 123, 394 ~1923), N.J.
Leonard and J.H. Boyer, ~. Orq. Chem., Vol. 15, 42 (1950), Oraanic SYntheses~ Coll., Vol. 5, 1055, P.A.S. Smith, Derivatives of_HYdrazine and Other HYdronitroqens Havinq -N-N- Bonds, 120-124 ~ 130-131, The Benjamin/Cummings Publishing Co. (1983), and S.R. Sandier and Waif Karo, OrGanic Functional Group PreParations, Vol. 1, 2nd Ed., .
, 457.
The compound of formula (I) is usually used in an -~
amount of from 0.0l to 50 g, preferably from 0cl to 30 g, ~ ~ -1332029 `

more preferably 0.5 to 10 g, per liter of a color developer.
The above-recited content of the compound of formula (I) is in the working developing solution. The replenisher for the color developer may have the same content of the compound of formula (I), or the compound of formula (I) may be stocked as a separate part and mixed on use.
The compound represented by formula (II) is described below in detail.
R5 represents a straight chain or branched alkylene group having at least one of and at least one kind of substituents selected from a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a sulfo group, a phosphono group, a sulfonyl group, a ureido group, an acyl group, an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamido group, a halogen atom, a cyano group, and a nitro group (e.g., 2-hydroxytrimethylene, 1-methoxypentamethylene). R5, R7, R8, and R9, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
Substituents for the alkyl or aryl group for R6, R7, R8, and R9 preferably include a hydroxyl group, an alkoxy . ~

group, an aryloxy group, a carboxyl group, an amino group, a sulfo group, a phosphono group, a sulfonyl group, a ureido group, an acyl group, an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamido group, a halogen atom, a cyano group, and a nitro group. These substituents may further have two or more of and two or more kinds of ubstituents per alkyl or aryl moiety. Of the functional groups contained in formula (II), a carboxyl group, a phosphono group, and a sulfo group may be in the form of a salt with an alkali metal (e.g., sodium, potassium) or a cationic atom or group (e.g., NH4~, Ca2~), and an amino group may be in the form of a salt with various acids (e.g., hydrochloric acid, nitric acid, phosphoric acid, oxal~c acid, acetic acid).
In formula (II), R5 preferably repre~ents a hydroxyl~
substituted alkylene group, an alkoxy-substituted alkylene group, an amino-substituted alkylene group, a sulfo-substituted alkylene group, and a ureido-substituted alkylene group. R6, R7, R8, and R9 each preferably represent a hydrogen atom, an unsubstituted alkyl group (e.g., methyl, ethyl, isopropyl), a hydroxyl-subQtituted : ,, alkyl group, an alkoxy-substituted alkyl group, a -carboxyl-substituted alkyl group, and a sulfo-substituted alkyl ~roup. ;`

- 28 - ;

The total number of the carbon atoms contained in R5, R6, R7, R8, and R9 is preferably 30 or less, and more preferably 20 or less.
The compound of formula (II) is preferably added to a color developer in an amount of from 0.1 to 20 g, more preferably from 0.5 to 10 g, per liter.
Specific examples of the compound of formula (II) are .;~
shown below for illustrative purposes only but not for .
limitation.

, .

.
~,.

- 29 ~

1~3202~

OH
1) 11 2N--CH ~CHCIl ~--NH

OH
CHa~ I /C~IJ
II --(2) N--CH 2CllCH s--N
CH~ \CII~

Cl120H
II --(3) H 2N ~ (CH 2) ~--CH ~ NH ~

CH zOH ::

(4) HsN--~CHs) ~--CH--NH2 ;~
~. . . .
~ ' ';''.~':' OH
II--(5) (HOCH2CHz~ NC112CHCH2N ~CH2CH20H~
fl~201~
II ~ (6) (HOCN 2CII ~ -h N.(Clls) ~ ~CH~N ~ CH2CH20H) 2 ~ -, , , '~

:
~332~29 :;

II--(7) (ItO2CCII~ ~ NC112CIICII~N ~ CHYCO2H) OH
II--(8) 1102CC112NNC112CIICH~NHCH2C0211 OH
II--(9) NaO2C--CII--NHCH2CHCH2NH--CHCOi Na NaO2C--CH2 Cl12CO2Na CH, OH CH, (10) NaO2C--CH--N--C112CIICI12--l--CHCO2Na NaOsc - cH~ , CH2CO2Na 011 ', ~ ~:
: II--(11) (Nao~scH2 ~2 NC112CIlCllsN~CH2SO~Na) OCH, Cl~ ~CHI ~;
2) / NCI1 2CIICI1 2N~

OH
` II--(13) (CH ,OCH 2CII ~ ~ NCH 2CIICH 2N (Cll 2CII 20CIJ ~) s ::

'`.

-~ ~

`~ ~

1332029 ::

II--(14) ~CII,OCH2CN2~2 N(CHz)4-CN~J~CH~CH20C11~)2 IOCH, ;;
II ~ (15) (Cll:~OCN~CH2 ~ NCI12CllCil~N (CH2CH~OCHa) 2 ~H~
--(16~ (HOCH2CH2 ~2 NC112CHCH2N (CH2CH20H) 2 8 ~:~

(17) (HOCH2CH2)2--HCH2CllCI12N~CllzC112011)2 N : CH j~ Cll 3 ~ `
N~ . ~`:
~ ~ Cll, ~ I ~ CII, II--(18) ~NCH2CNClliN~ ` -~: Clll ..... . Cll, :
SO,H C ;~
19)>NCH2CIICI12N/ ~ `-Cll, Cll `~:
:~ SO,II
I i , . II (20) `(tlO~CCII~) 2NCII~CIIGII~N (CII~CO~II) 2 :~ ;:

: .

~,.

: - :

OH
II- (21) ( ~ NCH~CHCH2N ~ ) OH
II - (22) (HO ~ NCH2CHCH2N ~ OH) : -.
,: .
OH
(23) ( ~ NCH~CNCH.N ~ ) ' .:
~: CH20H
(24) ~ NHtCH~ CH- NH

(25) ~ NN-CH:C Cll,NH ~ :~

~ ~; ,' "

:
: _ 33 - :~

1332029 :

II--(26) CH3 0~1 C~3 (~H2CH2N (`H2 (~H Cl`12 N CH2C~20H ~;
I I--( 2 7 ) :' ;
CH3 0~ C~J3 CH3 C) CH2 C~2 N CH2 C~l CH2 N C~2 CH2 0 CH3 I I --( 2E3 ) I ~J3 ~ H3 HO CH2 (,'H2 ~ CH2 CH (:`~12 (~J CH2 N Cl 32 C~12 011 ~ -( 2 S~ ) CH3 C~33 C~3 N 1 ~3 ()C~2( ~2NC~2CH-C~}2NCH~ 12 t 30 ) HOC~12CH2 CH2C~2C)~ .. ,~;,, ` ~ N -:~
C~13~ 1 ~CH3, N CH2 CH C~2 N~
C~3~ (,'~13 ( 3 1 ) 0~1 0~ , !~ . i CH3 ¦ I ,CH
~ N C~12 C ~1 C~ J 2 C~ ~'H;2 ~
CH~ ('H3 ., ;

. .

-- 3 4 - ' ,', ,'.

~332029 II--(32) O~ J OH
1~2N C~12 (~H ~'~2 Cl~ (,tl2N112 :: .
II --(~j3) ()H O~
(HO2CCH2)2NCH2CH(~2C~CH2N (C~2(~02H )2 ( 3 4 ) : ~ (,'113 C~12OH
; ~()C~12CH2N.- (Cl12)4-C~-NC~12CH2011 C~3 ( 35 ) C~20H :~
C~3 1 ,C H3 ~N- ((,'H2~-CH-N :~
3~ ~ C~H~ :

", ~' .

The compounds of formula (II~ are easily available as commercial products, or can be easily synthesized according to the processes described in Orqanic SYnthesis I, 102, ibid, II, 154, 328 and 558, and ibid, III, 370 and 800.
The compound represented by formula (III) is described below in detail.
The terminolo~y "dimer or higher polymer" as used in the definition of formula (III) means a bis-compound or polymer coupler comprisin~ two or more of the moiety represented by formula (III). The polymer coupler includes a homopolymer solely comprising a monomer unit represented by formula (III), preferably a monomer unit having a vinyl group (hereinafter referred to as a vinyl monomer) and a copolymer of such a monomer and a non-color-forming ethylenically unsaturated monomer which does not undergo coupllng with an oxidation product sf an aromatic primary amine developing agent.
The compound of formula (III) is a 5-membered ring-5-membered ring condensed nitro~en~containing heterocyclic ring coupler whose chromophoric nucleus exhibits . .
aromaticity isoelectric to a naphthalene rin~, and has a chemical structure generally referred to as "azapentalene".
Preferred of the couplers of formula (III) are lH- ~
imidazo~l,2-b]pyrazoles, lH-pyrazolo[1,5-b]pyrazoles, lH- `

-pyrazolo~5,1-c][1,2,4]triazoles, lH~pyrazolo[1,5-b]-[1,2,4]triazoles, lH-pyrazolo[1,5-d]tetrazoles, and lH-pyrazolo[l,5-a]benzimidazoles, represented by the following formulae ~IIIa), (IIIb), (IIIc), (IIId), (IIIe), and (IIIf), respectively. Particularly preferred of them are those of formulae (IIIa), (IIIc), and (IIId):

`~ ,;' :`

,"

~332~29 12 b~X R12 X

\N NH ~ IN~ Rl 4 ~;
H N J~
Rl 4 R13 ,.
(III a) (III b) . . .:
. . .
. .

(III c) (III d) ~N ~N~
8N N . )1~ ;

(III e) ( f) R13 - 38 - ;
.

1 3 3 ~ 0 2 9 In the above formulae (IIIa) to (IIIf), R12, R13, and R14 each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic 02y group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a ;
sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an -~
alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group; X
represents a hydrogen atomr a halogen atom, a carboxyl group, or a group which i5 bonded to the carbon atom at the coupling position via an oxygen atom, a nitrogen atom or a su~fur atom and is releasable on coupling; or R12, R13, Rl4, or X represents a divalent group at which the compound is dimerized to form a bis-compound.
When the moiety represented by formulae (IIIa) to ~IIIf) is in a vinyl monomer, Rl2, R13, and R14 represent a mere bond or a linking group, via which the moiety and a vinyl group are linked. `
More specifically, R12, R13r and Rl4 each represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine), , '~ ;' - 39 - ~
;,.

~332~29 ~;

an alkyl group (e.g., methyl, propyl, isopropyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-amyl-phenoxy)propyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonylethyl, cyclopentyl, benzyl), an aryl group ~e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), a heterocyclic group (e.g., 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), a cyano group, an alkoxy group (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-phenoxyethoxy, 2-methanesulfonylethoxy), an aryloxy group (e.g., phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, a heterocyclic oxy group (e.g., 2-benzimidazxolyloxy), an acyloxy group (e.g., acetoxy, hexadecanoyloxy), a carbamoyloxy group (e.g., N-phenylcarbamoyloxy, N-ethycarbamoyloxy), a silyloxy group (e.g., trimethylsilyloxy), a sulfonyloxy group (e.g., dodecylsulfonyloxy), an acylamino group (e.g., acetamido, benzamido, tetradecanamido, a-(2,4-di-t-amylphenyl)butylamido, r- ~ 3-t-butyl-4-hydroxyphenoxy)-butylamido, a-~4-(4-hydroxyphenylsulfonyl)phenoxy]-decanamido), an anilino group ~e.g., phenylamino, 2-;
chloroanilino, 2-chloro-5-tetradecanamidoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2- ;
chloro-5-[~-l3-t-butyl-4-hydroxyphenoxy)dodecanamido]-anilino), a ureido group ~e.g., phenylureido, N-butyl-N'-methylureido, methylureido, N,N-dibutylureido), an imido ' ' 1332~9 group (e.g., N-succinimido, 3-benzylhydantoinyl, 4-(2-ethylhexanoylamino)phthalimido), a sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino, N-methyl-N-decyl-sulfamoylamino), a carbamoylamino group (e.g., carbamoylamino, N,N-dimethylcarbamoylamino), an alkylthio group (e.g., methylthio, oc~ylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-(4-t-butylphenoxy)propylthio~, an arylthio group ~e.g., phenylthio, 2-butoxy-5-t-octyl-phenylthio, 3-pentadecyl-phenylthio, 2-carboxyphenylthio, 4-tetradecan-amidopheny1thio), a heterocyclic thio group (e.g., 2-benzothiazolylthio), an al~oxycarbonylamino group ~e.g., methoxycarbonylamino, tetradecyloxycarbonylamino) an aryloxycarbonylamino group (e.g., phenoxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino), a sulfonamido group ~e.g., methanesulfonamido, hexadecanesulfonamido, benzenesulfonamido, p-toluenesulfonamido, octadecane-ulfonamido, 2-methyloxy-5-t-butylbenzenesulfonamido~, a carbamoyl group (e.g., N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-, . I . , ~ i . ;.
methyl-N-dodecylcarbamoyl, N-~3-~2,4-di-t-amylphenoxy)-propyl~carbamoyl), an acyl group (e.g., acetyl, (2,4-di-t-amylphenoxy)acetyl, benzoyl), a sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, '''''"~

;,:

133~02~ ::

N,N-diethylsulfamoyl), a sulfonyl group (e.g., methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), a sulfinyl group (e~g., octanesulfinyl, dodecylsulfinyl, phenylsulfinyl), an alkoxycarbonyl group ~e.g., methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), or an aryloxycarbonyl group (e.g., phenyloxycarbonyl, 3-pentadecylphenyloxycarbonyl).
X represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine, iodine), a carboxyl group, or a group containing an oxygen atom at which it is bonded (e.g., : ` :
acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-., cyanophenoxy, 4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, a-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy), a group containing a nitrogen atom at which it is bonded (e.g., benzenesulfonamido, N-ethyltoluenesulfonamido, heptafluorobutaneamido, ~ ' , 2,3,4,5,6-pentafluorobenzamido, octanesulfonamido, p-~- cyanophenylureido, N,N-diethylsulfamoylamino, l-piperidyl, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl, 1-benzylethoxy-3-hydantoinyl, 2N-l,1-dioxo-3~2H)-oxo-1,2-benzoisothiazolyl, 2-oxo-1,2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl, 3,5-- 42 - -~

!
1332~29 diethyl-1,2,~-triazol-1-yl, 5- or 6-bromobenzotriazol~
yl, 5-methyl-1,2,3,4-triazol-1-yl, benzimidazolyl, 3-benzyl-l-hydrantoinyl, l-benzyl-5-hexadecyloxy-3-hydrantoinyl, 5-methyl-1-tetrazolyl, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), or a group bonded at the ionic atom thereof (e.g., phenylthio, 2-carboxyphenylthio, 2-butoxy-5-t-octylphenylthio, 4-methanesulfonamidophenylthio, 2,5-dibutoxyphenylthio, 4-methanesulfonylphenylthi~, 4-octanesulfonamidophenylthio, 2-butoxyphenylthio, 4-dodecyloxyphenylthio, 2-(2-hexane ulfonylethyl)-5-t-octylphenylthio, benzylthio, 2-cyanoethylthio, 1-ethoxycarbonyltridecylthio, 5-phenyl-2,3,4,5-, ;~ . .
tetrazolylthio, 2-benzothiazolylthio, 2-dodecylthio, 2 dodecylthio-5-thiophenylthio, 2-phenyl-3-dodecyl-1,2,4-triazolyl-S-thio).
:The divalent group as represented by R12, R13, Rl4, or J~ X, at which a bis-compound is formed, includes a substituted or unsubstituted alkylene group ~e.g., ;`
methylene, ethylene, l,10-decylene, -CH2CH2-O-C~2CH2-), a ~ ~:J. . !: i substituted or unsubstltuted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, ~ ~ ) CH3Cl i "

: :: :~ .j . ,^
~ - 43 -~332029 and -NHCO-Rl5-CONH- (wherein R15 represents a substituted or unsubstituted alkylene or phenylene group).
In the cases where the moiety represented by formulae (IIIa) to (IIIf) is contained in a vinyl monomer, the linking group as represented by Rl2, R13, or Rl4 includes a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, l,10-decylene, -CH2CH20CH2CH2-), a ~ubstituted or unsubstituted phenylene group (e.g., 1,4-CH3 C~phenylene, 1,3-phenylene, ~ , ~ ), ~ ~3 ~ C~
-NHCO-, -CONH-, -O-, -OCO-, and an aral~ylene group (e.g., -CN2 ~ CH2-, -CH2CH2 ~ CH2CH2-, -CH ~ CH2-)~
and a combination of these linking groups. ~ ~;
The vinyl group in the vinyl monomer may have a ~;~
substituent other than the moiety represented by formulae ~IIIa) to (IIIf). Preferred of such a substituent are a hydrogen atom, a chlorine atom, and a lower alkyl group having from 1 to 4 carbon atoms.
The non-color-forming ethylenically unsaturated monomer which does not undergo coupling with an oxidation product of an aromatic primary amine developing agent includes acrylic acid, a-chloroacrylic acid, a-alacrylic acid (e.g., methacrylic acid), and esters or amides of 13~2~29 these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetonacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, B-hydroxymethacrylate), methylenebis-acrylamide, vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g., styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone, sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl ,:;
alkyl ethers (e.g., vinyl ethyl ether), maleic acid, ~
maleic anhydride, maleic esters, N-vinyl-2-pyrrolidone, N-~ ;
vinylpyridine, and 2- or 4-vinylpyridine. These non-color-forming ethylenically unsaturated monomers may bej`;~
used~e~ither lndividually or in combination of two or more ~`
thereof.
For specific examples of these couplers and processes ~
for synthesizing them, the following references can be -;
referred to: JP-A-59-162548 for the compounds of formula (IIIa); JP-A-60-43659 or the compounds of formula (IIIb);'!. `'~
JP-B-47-27411 for the compounds of formula (IIIc); JP-A-59-171956 and JP-A-60-172982 for the compounds of formula (IIId); JP-A-60-33552 for the compounds of formula (IIIe);
and U.S. Patent 3,061,432 for the compounds of formula (IIIf).
To any of the compounds of formulae (IIIa) to (IIIf) is applicable the ballast group having high color forming properties disclosed in JP-A-58-42045, JP-A-59-214854, JP-A-59 - 177553, JP - A-59-177544, and JP-A - 59-177557.
Specific examples of the pyrazoloazole couplers which can be used in this invention are shown below for illustrative purposes only but not for limitation. .

,~

?'?' ` ' ' ' ' "' ' ' " ` ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' -~332~29 :

M - I ) C1oH2l (n) HO -~--SO,~- O!IICNH -~- (CN.) .
o 11 Jl, . ~ :, H 1~
(M - 2 ) I lO 21 ( ) CH~ ,.

RO-~--50.~3-OCIICR1-O--~CR.).~ C

\ 1 ( M--3 ) CH.
G4H9(n) ;
(t~C58 ~--~--Ol~CR1-~- ( C5H~ ~ (t~ N~ R

Cll. '~
I M - 4 ) (t) C4Hg - :~

C~.~O ~-IIRCC --~-OR

:~: N
CH .

( M--5 ) CH~ C~

,~ I J~ o (Cll~) . -~--NIICCHO -~--50~- OH

1 (n) . ~, 47 ~.,, 1332~29 IM- 6) C H ~ C ~

\ 11 N N C~ 11 ( ) N=--~CH~) ~ ~~~ NHCCHO ~~~ C5H11 (t) C6H1 3 ( (M-- 7 ) CH~ ce \ N ~\11 H
ol c~
(CH2) ~O~~ NHCCHO ~- SO~~ OH
C10 21 ( C
~: ~ ( M ~ 8 ) (t)C4Hg~C e \;N O ;

I?CH~) ~0~3~ PHCCIIO ~~3~ SO~- OH
C12 25 C~

t M - 9 ) CH~ O~--So,~3--OR

.; I \P ¦ O ~ (t) .
--~CH2) sO~~ !IHCCHO--~3~ C5H1 1 (t) C s R

~ ' ~332~29 ~

( M - I û ) (t~C4H

I ~ O
~CH~) .O~- RIICCIIO--~--NIISO~ OH
C10H2l (n) M -11) \N NH
Ct N~ ~CR~) ~O~- NHCCHO -~3--sO2-Q- OH

(M-12) 10 21( ) Cl - , ~--CONR C I ` -N HN
~"
tN2--1~3- NNCCHO -~3- 50~--ON

; ~ (M-13) C10H21(n) C~ ,H2,CNN - Q- c I c I `.
NH ~O~--SO .-H ~ N H

N~
Cll, , ~.,,,~.

'''.,' ,, 49 .~

~ - \

~ M - I 4 ) CN~ ce ~ ' \N~NH
OC ~ ' N ` H . -~3- NHCCHO - ~- SO, ~- OH
C1oH21 (n) C I
t M -15) : CH, C e CH o C5 11 N (CR~) 2C--NHCCHO--(~ C5U1 1 (t) ' C6H 1 3 tn) ,, .
: ( M--I~) CH~ c ;~ Nl~ . C~ 1 (t) ` ~ ~ (CHs) ~NHCCHO-~=~ 5 11 ( ) ~ C6 13( ) .-:
M - 17 ) Cll~ ~ ~C Q ..

N~ 5H1 ~ (t) ~(CH s) s OCCHO -~- C5 :' '~ ' ' - 5 0 - ~ .

, -:

( M ~

(CH~) sCH ~01~- SOs~ 011 1~ 0 C~5H1 1 ( ) (Cll s), - ~3- NIICCIlO - ~3 - C5H11 (t) ( ) (M--19) ~-;
C,H, O - C(CH,) ,CH,C(CII,), \ l NH C5H11 (t) (CHs), -~--NHCCKO -~~ C5Hl l (t) C6H1 3 (n~
(-M--20) CH,O C 2 ~

~: N \ ~\ . :
' 1 1 . C5H~ l (t) , '-.
(CHs) ~ ~~3- NHCCHO -~3~ C5H11 ~t) ~- ~ C6~ 3 ~n) ' ~, (M -21) (t)C4Hg O
O-~--OCHCNH-~- (CN,), C
O c l 2H23 ~n) ~( C H
' , . , ' :"' - 51 - .,:~:

133~029 M - 22 ) O O
NO -~3- OCIICNH -~3- (CH.) ,CNI~r~ O -~3- SO,CII, C4Hg(t) C~OH2~ (n) N\ /( Cll, (M-231 O O
HO -~- SO,~- OCHCNH -~- NHC- (CH,), ~C e C 1 0H2 ~ (n) \ N )\~

:~ . CH, (M--21) C- :
NO-~-SO~--O(CH,),O(CH~

NII

C H, ( M - 25 ) -`: C.H, (t)C5H11 ~~- OCHCNH C t - :
~ ~ o b~ ; 5 11 ( ) \II/~\XH

CH, - 5 2 ~

( M - 26) CH, O ~ - CN. .
~( ;':' '' \ Nl NH

I ~--C ~11 " t C ) C.H. ,H " (~) (M-27) ~( 11 U
QC~R~7(n) ' :"
(CN~)~NHSO~ Q
C, (M-28) C12H25 (n) H O - ~ - OC 1 C N R b~

ca, ~:
( M - 29) S ~ -RHSO~CH~ .

H ~
O \ N NH
HO - ~ - SO~ ~ - OCHCNH - ~ `

. 10 21 - 53 ~

t M - 30 ) CH~ ~ C I

rN ,1( N 11 llo-~-so~ oCliCRti-~- (Cllt)~ l l IOH21 (n) tM -31) C~ O
HO-~?--SOs~~ OCHC1---~3--(C1.~ C

M-32) C6H13(n) ,~
(t)c5~ -ocllt~-~-(c~ o~-so~3-ol C5H1 1 ( t ) \ N~jN H

t M - 33 ) Cli. C

i~ C6H13 (n) ' I tca~),--NliSOs~--NHSO,~ ~:
C--Clis~CtCRl)~
CH~

. :

54 ~ .:` ~
'`.~

1332~29 ....
; ":
- ~M--34) CH~ C
~ ", \ N /~\ N 11 O ~:
N--~CH~ IHCCH-04--9 C8H17(n) C ~ \=CNHSO ~

i CR~
~M-35) CH, CQ
~ ~'`.
N\H~'~NN
. :' N--~ I ~
(CH ~) ~--NNCCN - O~ ~ O;~ ~) s - OCR ~ -C~H~NRSO~
CR~-C-CH~-C(CH~)~
~ ~ Cll~ :~
(M-36) CR, C e : N\ ~ O ~ 8H17~n) OC 11 ' ';
N I
CNCH~ - NNC~- HHSO~- _~
CH~ CH~ - C - CH~ - C(CH~
Cll~

. ,;:

" ":

- 5 5 ~

( M - 37) CH, ~ C I

t~ H.OCH,CII, N CH-CHI-NHSO~ ~ 0 ~
CH, HHS0I y C.R,t~t) M - 38) CH~ ~ O ~

0 ~5 11( ) CR-CH~-NHCCH-0 ~ - C5H11(t) CH, C4H9 (n) ( M - 39) cll, ce - ~

\ N ~ NN
1--~ , ;, - CH-CH~-NHCCH-0 CH. C,.H~ ~ NHS0~ ~ - CH~
M - 40) CH~ C e N~ OC8H~7(n) CH.), - HHSD, ~
C - CH. - C(CH.).
~ ~ Cl~
:
`
; .

- 56 ~

~.3 ~

( M - 41) ~L~ C1, HH 8 1 7 ( ) CH~ HHSO~ ~

CH.
( M - 42) CH, C

\ Nl ~ ~R oc, n, .

CHCN.HHSO~ ~ OC.H~t ; CH, ~ NHSO. ~
C,H,.(t) ( M - 43) O~C,H.-C.H.O ~ S

a NN ;
oc,n, .
H -CH-C81NHSO~ - ~ O
CH, NHSO~
2:
, -C,H,7(~) '~ ., ' ' ~

~ ' .

i332~29 M - 44) OC4H~
CN~-O-CH~CH~0 S
. I~
I )1~ ~c.~ ~oc O
CR~)~NHSOs NHSOs C,H " ~t) M ~ 45) OC~H~
O-CHsCHsO S
; ~ r ~ CsHI7~t ~ OCH~

N
~CIIs)sNHSOs~(~
NHSO~ ~ - NHCOCH~

M ~ ~6) OC~H~
CH~SO~CH~)~O S
YOC"~

N~ N
CHs)s~llSOs ~/ ~ C~H~
~NHC-CHO ~ ~ CsH "
O C~HIl(t) ; . .:

58 ~
`,"'.`'.

13320~9 M - 47 ) C,ll,\ I
C ~ H ,~ NH ~C e \N NH
Nl~ 0;~2 ~ ~ - O Cil, CH-CH~-NHSO,~ O~
CH, NHSO,~

(M-18) C,H"~t) CH~
CH~\ I
f N - C - NS - C " H "

\NJJ\ NH
¦~ o~ r (CN2) ,NH -~ O~
HHSO
( M--4 9 ) \C<OC . H .
C~ S S4~_ OCI ,H~

\N ,r ~NiiCOC"R" (i) (C H ~ i H S O ~
h HCOC ~ ~ H " ( i ) CH~\
~C0 F
C~
; ! \NI~NH

J~S (C0 ) O Q C N
-CR-o -~3- C~R I ~ (t) . C

-' - 59 ~ ~

S M - S l ) CH ~ ~ C t ~(NH
OC . II .
(CH,) ,SO,~
C~HI7St) SM-52) OC.N.

~lli C"'"" . ~

C H . ), S O .
C.NI .

CH, ~ ,"C

N, Rl NN

~Jo - ~3-so~NN~3~cR~?~ `, .

t.l-54) CH
CH~
N

--SO NH~--CH
,R,7~t) C.H. ~`

' ~ ' ' ~ ~
'`' .
1332o29 M - 55 ) OC.II.
C~\C-~5~

OC,H" I I
~-SO~IIH~- (CH~ S - -C, H " ( t) ( M--56) CU~
C""''~

OC,H" I ¦
OC~H~.~-SO~Nil(CH.). .
- SO,NH
~ C""~
~M--51) CH, C e \NlI N

HO--~--SO~--OCHCONli~ (CHt) C " H ~, (M-55) ~ C ~ .
~CH ~C e i: i , j \ 11 ~; H ! : :
Csa (cH "~!
~: (CH,) ,C--CH. - --C~ j :
CH, 1 '.

~33202~

M - 59) O~C,II~
CH,O- ~CH,) ,O S4~
\=<C,H"(t) \HNll ~OC,II, , :, ~-so,(CH~
(CH,) ,C - CH~ - C - CH~
CH, (M--60) C,~H"
~Ob~5-CR-C?OC,II, C " H ~ ~ O - ~ - S O ~ N H C H ~ C H
CU, ',~ ~.
( M - 6 l j , CH,~ Cl ~`

C ~ ,~ N
~` ~CHCH,SO,CH,CH, :~
C, H "

S-62) D--~o C, R " ( ~

' ' "`"~'.

~':~

( M--63 ) -C H 2 --C H_ -C 11 ~ --C H ~ _ C O N ~/ ! c o C H

x: y = 50: 50 ~
` ~: \ ( by wei~ht , hereinaf ter the same ~ :
(M--64) ; -CH 2 --C CH . _ I Cll 2 --CH--CONN~N= ( ~ CO,CN~

x: y ~ 40: 60 :1, ; ' ' . .
'':
- 63 - : ~

~.

~332029 (M-65) -C~1 2 ~CII _ - - -Cll z -C~I - ~
CONIIl= I N I L CO~C,II,~

\~ 11 Y

C/~CHs x ~ .

x: y -50: 50 (M-66) - Cl~3 _ _ _ .
-Cllz--C~ _ -Cl12--Cll --CO 2C ~ H s ` .-:

~: . CONll~r ~( ~
J~ N N ~ Y
CH3 H ~N x ~ ~.

: i x: Y 55 ::

, ~.

,,'.",.'.
....
`,.
~'.' - 6 4 ~

13~2Q2~

( M ~ 67 ) -CH z --CH Cll I ~rCH z --CIJ----CONH I IN~ COzC~IJ~
~ )~ \ N ~ L J Y ~

C Q x ~
' ~

133~29 The coupler of formula (III) is used in an amount of from 2 x 10-3 to S x 10-1 mol, preferably from 1 x 10-2 to 5 x 10-1 mol, per mol of silver in a silver halide emulsion layer.
For the purpose of satisfying various photographic characteristics required for photographic materials, two or more different kinds of the coupler of formula (III) may be incorporated into the same layer, or the coupler of the same kind may be incorporated into two or more layers.
A color developer which can be used in the present invention contains a known aromatic primary amine color developing agent, preferably a p-phenylenediamine derivative. Typical examples of the p-phenylenediamine developing agent are shown below.
D~l: N,N-Diethyl-p-phenylenediamine D-2: 2-Amino-5-diethylaminotoluene `
D-3: 2-Amino-5-(N-ethyl-N-laurylamino)toluene ~
D-4: 4-[N-Ethyl-N-(B-hydroxyethyl)amino]aniline ~;
;~ D-5: 2-Methyl-4-[N-ethyl-N-(B-hydroxyethyl)amino]-aniline , ; I D-6: 4-Amino-3-methyl-N-ethyl-N-[B- `
(methanesulfonamido)ethyl]aniline D-7: N-(2-Amino-S-diethylaminophenylethyl)-methanesulfonamide D-8: N,N-Dimethyl-p phenylenediamine ~

" ~ .

- 66 - ~

-D-9: 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10: 4-Amino-3-methyl-N-ethyl-N-B-ethoxyethylaniline D~ 4-Amino-3-methyl-N-ethyl-N-B-butoxyethylaniline The p-phenylenediamine derivative recited above may be in the form of a salt with sulfuric acid, hydrochloric acid, sulfurous acid, p-toluenesulfonic acid, etc.
The aromatic primary amine developing agent is used in a concentration of from about 0.1 9 to about 20 g, preferably from about O.S g to about 10 g, per liter of the color developer.
If desired, the color developer may contain a sulfite type preservative, such as sulfites (e.g., sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite) and a carbonylsulfite adduct. However, it is preferable that the color developer contains substantially no sulfite lon for reasons stated above. The term "substantially no sulfite ion" as used herein means that the sulfite ion concentration in the color developer is no more than 5 x 10-3 mol, preferably of from zero up to 2 x 10-3 mol, i ~ per liter.

The color developer may contain other various preservatives in addition to the compound of formula (I), but, it is preferable that the color developer contains substantially no hydroxylamine preservative for reasons '~ ~
- 67 - -~

r .
., ' .
i332029 stated above. The term "substantially no hydroxylamine"
as used herein means that the hydroxylamine concentration in the color developer is no more than 0.01 mol, preferably of from zero up to 0.005 mol, per liter.
If desired, the color developer may further contain various additives. For example, it is preferable to add hydroxamic acids disclosed in JP-A-63-4313B, phenols disclosed in JP-A-63-44657, and JP-A-63-58443, a-hydroxyketones or a-aminoketones disclosed in JP-A-63-44656, and various sugars disclosed in JP-A-63-36244. In combination with these compounds, the color developer may also contain monoamines disclosed in JP-A-63-4235, JP-A-63-24254, JP-A-63-21647, JP-A-63-146040, JP-A-63-27841, and JP-A-63-25654, polyamines disclosed in Japanese Patent Application Nos. 164515/86, and 165621/86, JP-A-63-30845, JP-A-63-44655, and JP-A-63-26655, nitroxyl Eadicals described in JP-A-63-53551, alcohols described in JP-A-63-43140, and JP-A-63-S3549, oximes described in JP-A-63-56654, and te~tiary amines described in Japanese Patent Application No. 265149/86.
Further included in preservatives which may be added to the color developer if desired are various metals as described in JP-A-57-44148 and JP-A-57-53749, salicylic acid derivatives as described in JP-A-59-180588, alkanolamines as described in JP-A-54~3532, "~

1332~29 polyethyleneimines as disclosed in JP-A-56-94349, and aromatic polyhydroxy compounds as described in U.S. Patent 3,746,544. In particular, addition of the aromatic polyhydroxy compounds, trimethanolamine or the compounds disclosed in Japanese Patent Application No. 265149/86 is advantageous.
The color developer according to the present invention preferably has a p~ of from 9 to 12, more preferably from 9 to ll.O. The color developer can contain conventionally known developer components.
: ~-It is recommended to use a buffering agent for maintaining the above-recited pH range. The buffering agent to be used includes carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycine salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrates, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, tris-hydroxyaminomethane salts, and lysine salts. Particularly preferred among them are carbonates, phosphates, tetraborates, and hydroxybenzoates because they exhibit good dissolution property ànd superior buffering activity in a high pH region of 9.0 or more, give no adverse ..: ~.
influences on photographic performance properties, such as ~;-fog, when added to a color developer, and are cheap.
,.,''~':

: . . . .
.` ' .~ . -;

Specific but non-limiting examples of these preferred buffering agents are sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium tertiary phosphate, potassium tertiary phosphate, sodium secondary phosphate, potassium secondary phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
The amount of the buffering agent to be added to the color developer is preferably not less than 0.1 mol/~, more preferably from 0.1 to 0.4 mol/~.
The color developer can also contain various chelating agents as a suspension agent for calcium or magnesium or for improving stability of the color developer. The chelating agent to be used preferably include organic acid compounds, such as aminopolycarboxylic acids disclosed in JP-B-48-30496 and JP-B-44-30232; organic phosphonicfacids disclosed in JP-A-56-97347, JP-B-56-39359, and West German Patent 2,227,639; phosphonocarboxylic acids disclosed in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-126241, and JP-A-55-659506; and the compounds disclosed in JP-A-58 - 195845, JP-A-58-203440 and JP-B-53-40900.

Specific but non-limiting examples of these chelating a g e n t s a r e n i t r i l o t r i a c e t i c a c i d, d i e t h y 1 e n e t r i a m i n e p e n t a a c e t i c a c i d , e t h y 1 e n e d i a m i n e t e t r a a c e t i c a c i d , N , N , N -trimethylenephosphonic acid, ethylenediamine-N,N,N' ,N'-t e t r a m e t h y 1 e n e p h o s p h o n i c a c i d, t r a n s -cyclohexanediaminetetraacetic acid, 1, 2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, l-hydroxyethylidene-l,l-diphosphonic acid, and N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'~
diacetic acid.
These chelating agents may be used in combination of ~ ., .
two or more thereof, if desired. The amount of the chelating agent to be added is determined so as to be enou~h to sequester or deactivate metallic ions in the color developer and usually ranges from about 0.1 to about 10 9 per liter.
If desired, the color developer may contain an arbitrary development accelerator. However, from the standpoint of prevention of environmental pollution, convenience of the preparation of the developer, and prevention of color stain, it is desirable that the color developer contains substantially no benzyl alcohol as ,,." '.

-71~

development accelerator. The term "substantially no benzyl alcohol" as used herein means that the content of benzyl alcohol in the color developer is no more that 2 ml per liter, and preferably nil.
The above-described compounds according to the present invention manifest their marked effects particulary when used in the processing with a color developer containing substantially no benzyl alcohol.
Other development accelerators which may be used in the presen~ invention include thioether compounds as described in JP-B-37-16088, JP-B-37-5987, JP-B-38-7826, JP-B-44-12380, JP-B-45-9019 and U.S. Patent 3,813,247 p-phenylenediamine compounds as described in JP-A-52-49829 and JP-A-50-15554; quaternary ammonium salts as described in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429; amine compoundsi as described in U.S. Patents 2,494,903, 3,128,182, 4,230,796, and 3,253,919, JP-B-41 11431, and U.S. Patents 2,482,546, 2,596,926, and 3,582,346; polyalkylene oxidesi as described in JP-B-37-16088, JP-B-42-25201, U.S. Patent 3,128,183, JP B-41-11431, JP-B-42-23883, and U.S. Patent 3,532,501; and, in addition, l-phenyl-3-pyrazolidones, imidazoles, etc.
If desiired, an arbitrary antifoggant can be added to the color developer. The antifoggant to be used includes alkali metal halides (e.g., potassium bromide, potassium 1~320219 iodide) and organic antifoggants, such as nitrogen-containing heterocyclic compounds (e.g., benzotriazole, 6-nitrobenzimidazole, 5-nitrosoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-t h ia zo ly lm e t h y l b e n z i m i d a z ol e , i n d a z ol e , hydroxyazaindolizine, adenine).
However, the amount of these antifoggants, if added, is preferably minimized for reasons stated above. It is particularly desirable that the color developer contains substantially no bromine or iodine ion that gives great influences on photographic characteristics. The term "substantially no bromine or iodine ion" as used herein means that the concentration of a bromine ion or iodine . , ~ ion is up to 2.5 x 10-3 mol/~, preferably up to 1 x 10-3 '~
..-~. ~
mol/~, or up to 3 x 10-4 mol/~, preferably up to 1 x 10 4 ` ~:~
mol/~, respectively. '~'~
The color developer to be used in the present ~;';
invention preferably contains a brightening agent, preferably 4r4'-diamino-2,2'-disulfostilbene compounds, in an amount of up to 5 g/~, preferably from 0.1 to 4 g/~. ~
If desired, various surface active agents, such as ' aIkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids, may also ''"
be added to the color developer.

- 73 - ~
., ~ " ".

The color development processing according to the present invention is carried out at a processing solution temperature of from 20 to 50C, preferably from 30 to 40C, for a period of from 20 seconds to 5 minutes, preferably from 0.5 to 2 minutes.
The color developer is replenished at a rate of from to 120 nu, preferably 30 to 100 mL, per m2 of the photographic material. When the quantity of the replenisher is 50 mc/m2 or less, the overflow of the color developer can be substantially eliminated since the color ~ -developer is carried away together with the processed photographic materials or evaporated during processing. ~;
Desilvering generally comprises a combination of bleach and fixation, a combination of fixation and blix, a combination of bleach and blix, or blix, and any of these systems may be used in this invention. In particular, t~e effects of the present invention can be taken full advantage of by reducing the time of desilvering, e.g., to 2 minutes or less, preferably between 15 and 60 seconds.
In a bleaching bath or blix bath, any conven~ional I ' ~
bleaching agent may be used. Particularly recommended -;
bleaching agents are organic complex salts of iron (III), for example, complex salts with aminopolycarboxylic acids ( e.g. , et hy l en ediami n ete tra a cet i c a c i d , diethylenetriaminepentaacetic acid), aminopolyphosphonic - 74 ~

1332029 -:

acids, phosphonocarboxylic acids, or organic phosphonic acid~; organic acids (e.g., citric acid, tartaric acid, malic acid); persulfates; and hydrogen peroxide.
Among them, organic complex salts of iron (III) are particularly preferxed from the viewpoint of rapidness of processing and prevention of environmental pollution.
Specific examples of the aminopolycarboxylic acids, aminopolyphosphonic acids or organic phosphonic acids or salts thereof which are useful for preparing the organic complex salts of iron (III) are ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediamine-tetraacetic acid, nitrilotriacetic acid, cyclohexane-diaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid, as well as their salts with sodium, potassium, lithium or ammonium.
; Preferred of these iron (III~ complex salts are iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediamine~
tetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid becau~e of their high bleaching capacity.
These ferric ion complex salts may be used in the form of a complex salt from the first; or the ferric ion '- ~

- 75 - ;-~332029 complex may be formed in situ from a ferric salt (e.g., ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate, ferric phosphate) and a chelating agent (e.g., aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid). In the latter case, the chelating agent may be used in excess. Of the iron complexes, aminopolycarboxylic acid-iron complexes are preferred, the amount thereof ranging from 0.01 to 1.0 mol/~, preferably from 0.05 to 0.50 mol/L.
The bleach bath, blix bath and/or their prebathes may contain various bleaching accelerators, such as compounds having a mercapto group or a disulfide bond as described in U.S. Patent 3,893,858, German Patent 1,290,812, JP~
53-9S630, and Research Disclosures, No. 17129 (Jul., 1978); thiourea compounds as described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and U.S. Patent 3,706,561;
.
and halides of an iodine or bromine ion. The above-enumerated compounds are advantageous because of their excellent bleaching capacity.
The bleach or blix bath may further contain a re-halogenating agent, such as bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides ~e.g., potassium chloride, sodium chloride, ammonium chloride) and iodides (e.g., ammonium iodide~. If desired, they may furthermore contain one or more of ~332029 organic or inorganic acids or alkali metal or ammonium salt thereof which have buffering activity (e.g., boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid) or a corrosion inhibitor ~e.g., ammonium nitrate, guanidine).
The blix bath or fixer contains one or more of conventional fixing agents, i.e., water-soluble silver halide solvents, such as thiosulfates (e.g., sodium thiosulfate, ammonium thiosulfate); thiocyanates (e.g., sodium thiocyanate, ammonium thiocyanate), thioether compounds (e.g., ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol); and thiourea. A special blix bath containing the fixing agent in combination with a large quantity of a halide (e.g., potassium iodide) as disclosed in JP-A-55-155354 can also be employed. In the present invention, use of the thioculfates, particularly ammonium thiosulfate, i9 preferred.
A recom~ended amount of the fixing agent in the fixer . . I I !
is from 0.3 to 2 mol/L, preferably from 0.5 to 1.0 mol/L.
The blix bath or fixer preferably has a pH of from 3 to 10, more preferably from 5 to 9. ;
The blix bath may further contain other various additives, such as brightening agents, defoaming agents, ;~
....

- 77 - `

surface active agents, and organic solvents (e.g., polyvinylpyrrolidone, methanol).
The blix bath or fixer contains, as a preservative, a sulfite ion-releasing compound such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite), and metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite). The sulfite preservative is added in an amount of from about 0.02 to 0.50 mol/~, preferably from 0.04 to 0.40 mol/~, on a sulfite ion conversion. It is usual to use the sulfite as a preservative, but other preservatives, e.g., ascorbic acid, a carbonyl-bisulfurous acid adduct, and a carbonyl compound, may also be added.
If desired, the blix bath or fixer may further contain other additives, such as a buffering agent, a brightening agent, a chelating agent, a defoaming agent, and an antifungal agent.
In the processing of the present invention, the desilvering by fixation or blix is generally followed by ! washing and/or stabilization.
; The quantity of water for washing is selected from a broad range depending on the characteristics of the photographic material (for example, the kind of components used, e.g., couplers), the end use of the photographic ~.
~ ' material, the temperatu~e o~ water, the number of washing tanks (the number of ~tages), the washing system (a counter current system or a direct current system), and other various factors. For example, the relationship between the number of washing tanks and the quantity of water in a multi-stage counter current system can be decided according to the method described in Journal of the SocietY of Motion Picture and Television Enqineers, Vol. 64, pp. 248-253 (May, 1955). The number of stages in a multi-stage counter current system is usually 2 to 6, and preferably 2 to 4.
According to the multi-stage counter current system, since the requisite quantity of water can be greatly decreased, for example, to 0.5 L/m2 to l ~/m2 or even less, the effects of the present invention are remarkably produced. However, this system tends to allow bacteria to grow in the tank due to the increased retension time of water, resultin~ in deposition of the scum onto the photographic material. In order to solve this problem, the method of reducing calcium and magnesium in water as disclosed in JP-A-62-288838 can be effectively applied to ~:.
the present invention. It is also effective to use ' --isothiazolone compounds or thiabenzazoles as described in JP-A-57-8542; chlorine type bactericides (e.g., chlorinated sodium isocyanurate) as described in JP-A-61-: ...

- 79 - ~

: :

120145; benzotriazoles as described in JP-A-61-267761 (corresponding to European Patent 204197A); a copper ion;
and bacteriocides described in Hiroshi Horiguchi, Bokin Bobaizai no Kaqaku, Eisei Gijutsukai (ed.), Biseibutsu no Genkin, Sakkin, Bobai Gijutsu, and Nippon Bokin Bobai Gakkai (ed.), Bokin Bobaizai Jiten.
The washing water can further contain a surface active agent as a wetting agent or a chelating agent ~e.g., EDTA) as a water softener. -The above-described washing step may be followed by or substituted by treatment with a stabilizing bath. The stabilizing bath to be u~ed contains compounds having functions to stabi~ize the photographic imagej for example, aldehyde compounds (e.g., formalin), buffering agents for adjusting the film to a pH suitable for dye stabilization, or ammonium compounds. The - above-enumerated various bactericides or antifungal agents can ~ : .
~; also be used for preventing growth of bacteria in the bath --~
or imparting antifungal properties to the processed photographic material.
The stabilizing bath may further contain a surface ~ active agent, a brightening agent, and a hardening agent.
-~ In the case where the photographic material is subjected to stabilization directly from the desilvering , 133~al29 processing, any of the known techniques described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be applied.
It is also preferable to use a chelating agent, e.g., l-hydroxyethylidene-l,l-diphosphonic acid and ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.
In the present invention, so-called rinsing solution may be used as washing water or stabilizing bath after desilvering.
During the washing or stabilization step, the pH of the processing solution is kept between 4 and 10, preferably between 5 and 8. The temperature, though varying depending on the end use and characteristics of the photographic material and the like, usually ranges from 15 to 45C, preferably from 20 to 40C. The processing time is arbitrary, but the effects of the present invention become significant with the time being shorter. A preferred time is from 0.5 to 4 minutes, more preferably from 0.5 to 2 minutes. The smaller the quantity of a replenisher, the better the results obtained in terms of running cost, reduction of a waste liquid, ease on handling, and manifestation of the effects of the present invention. More specifically, a recommended quantity of the replenisher is set at 0.5 to 50 times, preferably 3 to 40 times, the amount per unit area which .

~332029 has been carried over from the prebath. Alternatively, a recommended quantity of the replenisher is 1 ~ or less, preferably 500 mu or less, per m2 of the photographic material. The replenishment may be effected either continuously or intermittantly.
The processing solution which has been used for washing and/or stabilization may be recycled to the prebath. In one embodiment, the overflow of washing water, which is reduced by a multi-stage counter current system, is made to flow into the blix bath (i.e., the prebath), while replenishing the blix bath with a concentrated solution, to thereby reduce the amount of waste liquid.
The method of the present invention can be applied to any type of photographic processing. For example, the method is applicable to processing of color papers, color reversal paper~, color direct positive light-sensitive materials, color positive films, color negative films, color reversal films, and so on. In particular, application to color papers and color reversal papers is suitable.
The silver halide color photographic materials which `~
are subject to the processing method of the present invention will be described below.

~,~

13320~9 It is essential that the photographic material contains various color couplers. The terminology "color couplers" as used herein means compounds capable of coupling with an oxidation product of an aromatic primary amine developing agent to form a color. Useful color couplers typically include naphthol or phenol compounds as cyan couplers; pyrazolone or pyrazoloazole compounds as magenta couplers; and open-chain or heterocyclic keto-methylene compounds as yellow couplers. Specific examples of these cyan, magenta, and yellow couplers are described in patents cited in Research Disclosure ~RD), 17643, VII-D
(Dec., 1978) and ibid, 18717 (Nov., 1979).
It is preferable that the color couplers to be incorporated into the photographic material have a ballast group or are polymerized and are thereby non-diffusing.
Two-equivalent color couplers in which the coupling site is substituted with a releasable group are preferred to four-equivalent color couplers in which the coupling site is substituted with a hydrogen atom because the requisite silver coverage can be reduced, thereby producing greater~
effects of the present invention accordingly.
Couplers which produce a dye showing moderate diffusion, colorless compound forming couplers, so-called DIR couplers capable of releasing a developing inhibitor on coupling reaction, or couplers capable of releasing a .

.

1332~,~9 development accelerator on coupling reaction may also be used.
The yellow couplers which can be used in the present invention typically include oil-protected type acylacetamide couplers. Specific examples thereof are described in U.S. Patents Z,407,210, 2,875,057, and 3,265,506. As stated above, 2-equivalent yellow couplers are preferred. The 2-eguivalent yellow couplers typically include those having oxygen atom linked releasing groups ;
as described in U.S. Patents 3,408,194, 3,447,928, 3,933,501, and 4,022,620 and those havin~ nitrogen atom linked releasing groups as described in JP-B-58-10739, U.S. Patents 4,401,752 and 4,326,024, RD 18053 (Apr., 1979), Bri.tish Patent 1,425,020, West ~erman Patent Application (OLS) Noc. 2,219,917, 2,261,361, 2,329,587, and 2,433,812. a-Pyvaloylacetanilide couplers are excellent in dye fastness, particularly to light. a-Benzoylacetanilide couplers are excellent in color density. ;~
The magenta couplers which can be used in this invention include oil-protected type indazolone or cyanoacetyl couplers, and preferably pyrazoloazole couplers, such as 5-pyrazolone couplers and pyrazolotriazole couplersO Of the 5-pyrazolone couplers, those in which the 3-position is substituted with an ;~

, ~332029 ~ ~

arylamino group or an acylamino group are preferred in view of hue and density of the color developed. Typical examples of such 5-pyrazolone couplers are described in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653~ 3,152,896, and 3,936,015. Preferred releasable groups for the 2-equivalent 5-pyrazolone couplers include nitrogen atom linked releasing groups as disclosed in U.S.
Patent 4,310,619 and arylthio groups as disclosed in U.S.
Patent 4,351,897. 5-Pyrazolone couplers having the ballast ~roup disclosed in European Patent 73,636 provide high densities.
Pyrazoloazole couplers which are particularly preferred in the present invention include pyrazolo-benzimidazoles as described in U.S. Patent 3,369,879, and more preferably pyrazolo[5,1-d][1,2,4]triazoles as described in U.S. Patent 3,725,067; pyrazolotetrazoles as described in RD 24220 ~Jun., 1984); and pyrazolopyrazoles as described in RD 24230 (Jun., 1984). From-the viewpoint of freedom from undesired side absorption of yellow and light-fastness of the developed dye, the imidazolo[l,2-d]pyrazoles disclosed in European Patent 119,741 are preferred. The pyrazolo~l,5-b][1,2,43triazoles disclosed in European Patent 119,860 are particularly preferred.
The cyan couplers which can be used in the present invention include oil-protected type naphthol and phenol .. - ~;.
~ - 85 -~ ~32029 coupler Typical and preferred examples thereof are naphthol couplers as disclosed in U.S. Patent 2,474,293, and 2-equivalent naphthol couplers having oxygen atom linked releasing groups as disclosed in U.S. Patents 4,052,212, 4,146,396, 4,228,233, and 4,296,200. Specific examples of the phenol couplers are given in U.S. Patents 2,369,929, 2,801,171, 2,772,162, and 2,895,826. Cyan couplers providing a dye resistant to moisture and heat are preferably used in this invention. Typical examples-of su~h cyan couplers include phenol cyan couplers having an alkyl group containing 2 or more carbon atoms at the m-position of the phenol nucleus as disclosed in U.S. Patient 3,772,002, 2,5-diacylamino-substituted phenol couplers as disclosed in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, and Japanese Pa~ent Application No. 42671/83, and phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position as disclosed in U.S. Patents 3,446,622, 4J333,999, 4,451,559, and 4,427,767. ! i The 2-equivalent cyan, magenta, or yellow couplers which are preerred for use in the present invention ~particularly from the standpoint of minimizing changes of photographic characteristics, such as gradation, can be ~ ~: ' ' .;' ' ~3:3~

represented by the following formulae (IV) or tv); (VI);
or (VII); respectively.

OH
R23 ~ HCO 21 R22 ~ (IV) ' OH I
26~b, NHCOR24 (v) ~ .

,R2s CON '~

< R2 8 ; ~NH ~ ~VI) (R27)n 9 ~ ;:
~ R29 !~ : !
CH, I (VII) ; CH3--I -CO IH3 CH, Y5 In formulae (IV) and (V) representing cyan couplers, R2l, R24, and R25 each represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aromatic amino group, or a substituted or unsubstituted heterocyclic amino group; R22 represents a substituted or unsubstituted aliphatic group; R23 and R26 each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aliphatic oxy group, or a substituted or unsubstituted acylamino group; or R22 and . .
:~ R23, or R2s and R26 are taken together to form a 5- to 7-membered ring; and Yl and Y2 each represents ~a halogen :~ atom, or a group which is released upon coupling reaction `~
w:ith an oxidation product of a developing agent; or R2I, 2l R23, Yl, R24, R2sr R26~ or Y2 represents a mere bond or :~
,: :~. :.
;~ a dlvalent linking group to form a dimer or higher ~--~; polymer.
In formula (VI) representing magenta couplers, Rz7 , , , ' ! ' ,:~
represents a group capable of substituting a benzene ring; .
~;~ R28 represents a halogen atoml an alkoxy group, or an .
~ . .
: alkyl group; R2g represents a substituted or unsubstituted phenyl group; and Y3 has the same meaning as Yl or Y2 in ;;.
formulae (IV) or (Vj; and n is 1 or 2; or R27, R2g, R29, or ~`~

133~029 Y3 represents a mere bond or a divalent linking group to form a dimer or higher polymer.
In formula (VII) representing yellow couplers, Q
represents a substituted or unsubstituted N-phenyl-carbamoyl group; and Y5 has the same meaning as Yl or Y2 in formulae tIV) or (V); or Q or Y5 represents a mere bond or a divalent linking group to form a dimer or a higher polymer.
The term "aliphatic group" as used herein means a straight chain or branched or cyclic alkyl, alkenyl or alkynyl group.
In formulae (IV) to ~VII), the releasable group as represented by Yl/ Y2, Y3, or Y5 includes a group connecting the coupling active carbon atom and an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic, aromatic or heterocyclic sulfonyl group, or an aliphatic, aromatic or heterocyclic carbonyl group via an oxygen atom, a nitrogen atom, a sulfur atom, or a carbon atom; a halogen atom; an aromatic azo group; etc.
The aliphatic, aromatic or heterocyclic groups contained , in these releasable groups may be substituted with one or more substituents, which may be the same or different, selected from those acceptable for R21 (hereinafter described~. The substituent(s) may further be substituted ~-with the substituent acceptable for ~21.

1332029 :

Specific examples of these coupling releasable groups are a halogen atom ~e.g., fluorine, chlorine, bromine), an alkoxy group (e.g., ethoxy dodecy l ox y , methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), an aryloxy group (e.g., 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), an acyloxy group (e.g., acetoxy, tetradecanoyloxy, benzoyloxy), an aliphatic or aromatic sulfonyloxy group (e.g., methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (e.g., dichloroacetylamino, heptafluorobutyrylamino), an aliphatic or aromatic sulfonamido group (e.g., methanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy group ~e.g., ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy), an aliphatic, aromatic or heterocyclic thio group te.g., ethylthio, phenylthio, tetrazolylthio), a carbamoylamino group (e.g., N-methylcarbamoylamino, N-phenylcarbamoylamino)r a 5- or 6-membered nitrogen-containing heterocyclic group (e.g., imidazolyl, pyrazolyl, triazolyl, tetrazolyl, l,Z-dihydro-2-oxo-1-pyridyl), an imido group (e.g., succinimido, hydantoinyl), and an aromatic azo group (e.g., phenylazo), each of which may be substituted with substituents selected from those acceptable for R2l. In addition, the couplers having a i332029 releasable group bonded via a carbon atom include bis-type couplers obtained by condensating 4-equivalent couplers with aldehydes or ketones.
The releasable groups may contain a photographically useful group acting as a development inhibitor, a development accelerator, or the like.
Preferred combinations of releasable groups in the respective formula will be described later.
The cyan couplers of formula (IV) and (V) can be synthesized by known processes. For example, the cyan couplers of formula (IV) are synthesized by the processes described in U.S. Patents 2,423,730 and 3,772,002, and the cyan couplers of formula (V) are synthesized by the processes of U.S. Patents 2,895,826, 4,333,999, and 4,327,173.
In formulae (IV) and (V), R2l, R24, and R2s each preferably represents an aliphatic group having from 1 to 36 carbon atoms, or an aromatic, heterocyclic, aromatic amino or heterocyclic amino group having from 6 to 36 carbon atoms, each of which may be substituted with a substituent(s) preferably having up to 24 carbon atoms, more preferably up to 12 carbon atoms, e.g., an alkyl group, an aryl gr,oup, a heterocyclic group, an alkoxy group, an aryloxy group, an alkenyloxy group, an acyl group, an ester group, an amido group, a sulfamido group, ~?, an imido group, a ureido group, an aliphatic or aromatic sulfonyl group, an aliphatic or aromatic thio group, a hydroxyl group, a cyano group, a ~arboxyl group, a nitro group, a sulfo gorup, and a halogen atom.
The terminology "aliphatic group" as used herein means a saturated or unsaturated, and straight chain, branched, or cyclic aliphatic hydrocarbon group and includes an alkyl group, an alkenyl group, and an alkynyl group.
Typically included therein are methyl, ethyl, butyl, dodecyl, octadecyl, eicosyl, isopropyl, t-butyl, t-octyl, t-dodecyl, cyclohexyl, cyclopentyl, allyl, vinyl, 2-hexadecenyl, and propargyl.
R22 preferably represents an aliphatic group having from 1 to 20 carbon atoms, which may be substituted with a substituent(s) selected from those enumerated above for R2l-R23 and R26 preferably represents a hydrogen atom, a halogen atom, an aliphatic group having from 1 to 20 carbon atoms, an aliphatic oxy group having from 1 to 20 carbon atoms, or an acylamino group having from 1 to 20 carbon atoms. The aliphatic, aliphatic oxy, or acylamino group may be substituted with a substitutent(s) selected from those enumerated above for R
R22 and ~23 in formula (IV) and R25 and R26 in formula (V) may be taken together to form a 5- to 7-membered ring.

r~ ~

1332~

The compounds of formulae (IV) and (V) include dimerized or polymerized couplers formed at one or more of R21, R22, R23, and Yl in formula (IV) or at one or more of Rz4, R25, R26, and Y2 in formula (V) independently or in cooperation. In the dimerized coupler, the group at which it is formed represents a mere bond or a divalent linking group (e.g., an alkylene group, an arylene group, an ether group, an ester group, an amido group, etc., or a combination of these divalent groups). In the oligomer or polymer coupler, the groups at which it is formed are preferably in the polymer main chain or bonded to the polymer main chain via a divalent group, such as those described above. The polymer coupler may be either a homopolymer of the coupler derivative or a copolymer comprising such a coupler derivative and other non-color forming ethylenically unsaturated monomer(s) (e.g., acrylic acid, methacrylic acid, methyl acrylate, n-butylacrylamide, ~-hydroxymethacrylate, vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride, N-vinylpyrrolidone).
R21 in formula (IV) and R25 in formula ~V) each more preferably represents a substituted or unsubstituted alkyl or aryl group. The substituent for the alkyl group preferably includes a substituted or unsubstituted phenoxy group (the substituent therefore preferably includes an alkyl group, an alkoxy group, a halogen atom, a sulfonamido group, and a sulfamido group) and a halogen atom. The aryl group preferably includes a phenyl group substituted with at least one of a halogen atom, an alkyl group, a sulfonamido group, and an acylamino group.
R24 in formula (V) more preferably represents a substituted alkyl group or a substituted or unsubstituted aryl group. The substituent for the alkyl group preferably includes a halogen atom. The aryl group preferably includes a halogen atom. The aryl group preferably includes a phenyl group susbtituted with at least one of a halo~en atom and a sulfonamido group.
R22 in formula (IV) more preferably represents a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, and most preferably an alkyl group having ~
from 2 to 4 carbon atoms. The substituent for the alkyl , group preferably includes an alkyl or aryloxy group, an acylamino group, an alkyl or arylthio group, an imido ~;;
group, a ureido group, and an alkyl or arylsulfonyl group.
R23 in formula (IV) more preferably represents a hydrogen atom, a halogen atom (fluorine or chlorine being particularly preferred), or an acylamino group, with a halogen atom being the most preferred.
. :;

- 94 - ~

1332~29 R26 in formula (V) more preferably represents a hydrogen atom, an alkyl or alkenyl group having up to 20 carbon atoms, and most preferably a hydrogen atom.
In formula (V), it is preferable that R25 and R~6 are taken to~ether to form a 5- or 6-membered nitrogen-containing heterocyclic ring.
.
In formulae (IV) and (V), Yl and Y2 each preferably represents a halogen atom, more preferably a chlorine atom.
The cyan couplers of formula (IV) and (V) may be used ~`~ either individually or in combinations of two or more `~ thereof.
Specific and preferred examples of the cyan couplers ; of formulae (IV) and (V) are shown below.

~ , .~ :

~ ..
~ 1 ' i j ` ' !

:"; , ;' '"~ ~ ' ' ' '~
~ 95 ~

~3320~

( C ~

~ C12 H 5~( t) C s H

CH3/~ (t)CsH

CQ
(C- 2 ) C Q ~ NHCOCHO ~ (t)C,H "

. .
,. ... .

( C - 3 ) C e ~ HCOCHO ~(t) Cs H "

CaHs~ (t)CsH
CQ

( C--4 ) OH
C ~N H C O--C (C H 3 ) 3 1 1 ~
C I s H 31 /~j~ ' ~;
c.e ( C - 5 ) OH CI~Hs ~
C ~ ~ HCOCHO ~ C~Hs(t) C~Hs ~ ~ (t)C~Hs C ~
~, ( C - 6 ) ~:
OH CIl~H2s F ~ YHCOCHO ~ OH

CH ~ ~ (t)C~Hs 3 1 ` `

( C - 7 ) C Q ~ HCO(CH~)~O ~ (t)C~H~

(t)C6H~
' ,. ~ ! ~ C~Hs C Q

- 97 ~
" ~:

..

` 1332029 ( C ~ 8 ) C ~ ~ 'RCOCHO ~ (t~CsH

CH3CONHCH2 ~ (t)CsH~
C Q

( C - 9 ) . ,~

CH~CONH ~ YHCOCHO ~ (t)CsH~

C~Hs~J (t)CsH~I -( C - 1 0 ) ' ', ~.

O ~ N ~ ~HCO ~ `~

NHCOCHO ~ (t)CsH

C Q (t)CsH~!

~ '~
-- g 8 ( C--11) OH
C Q~NHCOC I 3 H 2 7 CQ

( C--1 2 ) O H
~,NHCOC3F7 -~

( t) C s H ~ ~ 4~O CHCON H ~
\~( CQ ~;
(t) CsH

: ( .C - 1 3 ) C,l~SO~l~OCIJCONH J~ ;

~.

~33~29 ( C ~ 1 4 ) (t)CsHII~ ClsH
CQ
C Q --( C -153 d~N HCO e3~ t) C ~ H s Cl1 aHas ~l ¦J
~OCHCONH ~ ~
~~ C Q ~ :
C Q

( C--16 ) O H
NHCO ~ :

(C~H~) ~NSO~NH--~OCHCONH J~j C

,.~,,"

( C--17) (t)CsH~ ilHCO
: CQ
C Q

( C--18) F

~; ~NHCO ~F

~OCHCONH J~ I F F

( t) C s H I I

, ~ -( C--1 9 ) NH CO ~3CO OC ~ H
C, 1 2 H 2 5 ,I IYC ~ OCHCONH ~ ~ j , ~ .
CQ

- 1 ' . '.
"` , ~ ., ~.,1 :~- .. ..

~ ' ".. -"'.
: -- 101 --(C -20) (t)C H. C~H~s ~ NHCo HO ~ OCHCONH ~ ~ ~HSO,[H, ( C - 21) C,H7 ~ NHCO
C6H,3 ¦
~; (t~C5H " ~ OCHCONH

C Q C Q
( C--2 2 ) CONH ~ ~
NHSO 2 ~ CH 3 ; (i)~CI.H35CO~H `

. ~

13132~2~ :

( C--23 ) C,HS~

( t ) C s H I I ~-H

~C-2~

HCO~3 :
~N H S O a C 1 6 tl a C Q
; .
: (C-25) ~HCO IHO ~

C Q (t) Cs H I l ;

~` . , .'"':
.: .;

` ~-- 1332~29 ( C -26) ~, N HCO ~/ ~
' ( t) C 5 H " ~:

H ~ NHCOCHO ~(t) CsH " ~ ;~
C Q I \=/
:~ C 2 H 5 (C--27) O H
~, NllCO ~

o ~ ~J NHSO2C, 6H3~ ;
~: H
C Q

C-28) ::
.

~ `I H COCIJO ~ t ) C, H " ~

~';;
.

~`` ~ ~
1332~29 - ::

( C -29) H~ C~-~H ~

:~ ' C O ;~ :, - (C-30) ~:

CH7 \~, ~HCO ~

-- N~ NHS2C-6H33 C O - ': '~'''"`'~

( C -3 :(t)C,H"g~_ C ~HHcoNH~

~ i tt)C5H~I, C

`~ " ''"'' ~

~"~
- 1 0 5 _ :
'"'''':"';

1332o29 ( C--32) ,~ 9 H c o a H ~ c e (t)C.H.7 ~ 0CHCO.~H ~ C Q
C Q
(t)C8H,7 ( C - 33) SO.C,H, (t)C,H " ~ OCKCONH ~ (t)C.H "

~ 1 . I `

~ 106 ~

:` `

The magenta couplers represented by formula (VI) are disclosed in JP-A-60-262161 and JP A-60-238832.
In formula (VI), R29 represents a phenyl group, preferably a substituted phenyl group having one or more substituents selected from a halogen atom, an alkyl group (preferably having from 1 to 5 carbon atoms), an alkoxy group (preferably having from 1 to 5 carbon atoms)l an aryloxy group, an alkoxycarbonyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfonamido group, and an acylamino group. A preferred substituent is a halogen atom, and particularly a chlorine atom.
The coupling releasable group as represented by Y3 specifically includes a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, and a group represented by formula~
N Z, wherein Z represents an atomic group comprising atoms selected from carbon, oxygen, nitrogen and sulfer atoms, which is necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring in cooperation with the nitrogen atom.
R28 represents a halogen atom, an alkoxy group (preferably having from 1 to 5 carbon atoms), or an alkyl group (preferably having from 1 to 5 carbon atoms), '~''"''-'' ''".,' preferably a halogen atom, and more preferably a chlorine atom.
R27 is a group capable of substituting the benzene ring, and n is 1 or 2. When n is 2, the two R27 groups may be the same or different. The group as represented by R27 includes a halogen atom, R'-, R'O-, R'l_N_, R'SO2N~
O R" R"
R"OC-N-, R'COO-, R'-N-CO-, R'-NSO2-, R'O-CO-, R-N-CON- , Il l l l i I ,, O R" R" R" R" R"' and ~ ~ , wherein R', R", and R"', which may be the O :
same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. Preferred of these groups are O

R'CONH-, R'SO2NH-, and ~ - .
R
o Specific examples of the magenta couplers of formula (VI) include those disclosed in JP-A-60-262161 with compound Nos, of M-l through M-37 and those disclosed in JP-A-60-238832 with compound Nos. of M-l through M-34, as well as mixtures of two or more of these compounds.
Preferred among them are the compounds listed below and ~, .

the compounds used in the working examples hereina~ter given.

m - 1 C Q

~/ ~ NH S - CIHCOOC H
C,2H250 ~ SO2NH
N O
- C

C

m - 2 C Q O~Hg ` :

NH ~ S

C,3H27CONH \N O C~H,~(t) C Q ~ C Q

C Q

:

- 109 - .~;.

m--3 O(CH 2 ) ~ CONHC~H.

~ NH S ~
(t)C.H,I ~ Cl Hs ~ ~ o C.H,7tt) C.N" (~) ce~e ce m--4 U(CH2)~SO2NHC2H5 CQ
~ NH S ~ / ~
: ~ (t)C.~-I ~ OCHCONN ~ C.H,7(t) C.N " (t) ce~e CQ

m - 5 O(CN,),COOC2H, CQ :

(I)C,N " ~ DCN,CONN ~ ~ .N,7(~) C,H" (t) C~ ~ Q

C~

m - 6 CQ
NH S(CH,3 ~CON /
~ IC4H. ~ ~ ~ C7Hs (t) C.H" ~ OCHCONH N
C,H" (t) CQ

OCH, :
m - 7 OC~H.

DH ~ S ~ ~
N~ N o C.. H,. (t) ;
O ~ C
CH=CHC,,H~, ~
~: C ~ ".

m - 8 CQ O-CH.CU20C~2CH20CH, NH S ~
J
C "H.. CONH N~ N "~ F. H, Z ( t) c e~

`~

:: ' ~3320~9 m--g CONH~ 1~ 0 t c --lci~

Cl$fe .

~ m--10 C~Hs N0~0~Ni~

d~c e CODC, ~ H ~

' ; ~ OCH~

m--11 C ~ O (Cfl~) ~COOC~Hs ~NH S~
(t~CsNll~OCH~rONH ~ C~H~7(t) C~H~t) ce~ 8 c e ' ,' , :. .
. ,.
N N
"~
\/ ;'' Z
O , .

N

n o ~ ~
~ _ .'' '' !.
: O ~T :

: `' y - ;'''~

....

- 113 ~

.

With respect to the yellow couplers represented by formula ~VII), descriptions of JP-A-63-11939 can be referred to. In formula (VII), the substituent or substituents, which may be the same or different, for the phenyl nucleus of the N-phenylcarbamoyl group as represented by Q can be selected from those enumerated for the aromatic groups as represented by R2l.
A preferred N-phenylcarbamoyl group for Q includes those represented by formula (VII-A): --CO~H ~. (VII-A) NHCOR34 ;~

wherein Gl represents a halogen atom or an alkoxy group;
G2 represents a hydrogen atom, a halogen atom, or a substituted or unsubstitutued alkoxy group; and R
represents a substituted or unsubstitu~ed alkyl group. ~`~
In formula (VII-A), substituents for the alkoxy group ~, ~ ., .
(G2) or the alkyl group (R34) typLcally include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, ~ an amino group, a dialkylamino group, a heterocyclic group - ~ (e.g., N-morpholino, N-piperidino, 2-furyl), a halogen ~ atom, a nitro group, a hydroxyl group, a carboxyl group, a : :.
~ sulfo group, and an alkoxycarbonyl group.
'~;; ,' ' ~','',.'.
- 114 - ~
~: ","' .

The releasable group as r.epresented by Y5 preferably include those represented by formulae (X) to (XVI) -OR40 (X) wherein R40 represents a substituted or unsubstituted aryl -~:
group or a substituted or unsubstituted heterocyclic group.

. . N'N~--R
~ / 41 (XI) R 42 ~:

N ~ ~ ~-:~ \\ // (XII) ~
~ - ~, ,:
: 42 .

wherein R41 and R4z, which may be the same or different, each represents a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsufinyl group, a carboxyl group, a sulfo group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted heterocyclic group.
.
O ~ N ~0 , 1 (XIII) - ~, : wherein Wl represents a non-metallic atom group necessary for forming a 4- to 6-membered ring together with the ,, : moiety O ~ N ~ O . ~;

,~. ..
Of the releasable groups of formula (XIII), preferred are those represented by formulae ~XIV) to (XVI):

P ~N yO (XIV) R 43 ~ - N
R544 45 ;`~:

' , ~` ' ,.'.. ''"

: - 116 -;;", o ~",Y ~ o ' ' R43 --~ W2 ~ XV) R

O,~,,N ~0 N ~
R 47 (XVI) 4~

wherein R43 and R44 each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxyl group; R45, R46, and R47 each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group; and W2 represents an oxygen atom or a sulfur atom.
The yellow couplers of formula (VII) can be synthesized in accordance with the processes described, e.g., in JP-A-54-48541, JP-B-58-10739, U.S. Patent `!;: ~ ` ' i , , i ~
4,326,024, and Research Disclosure No. 18053.
~" Specific and preferred examples of the yellow couplers of formula (VII) are shown below.
~ -' ~ '.
.

-\ 1332029 (Y- 1 ) CQ

O=C ' `C=O
- N CH
/~\ / \ ' ~CH2 OC2Hs ~: ,. , ,''' (Y 2 ) ~ :;

...

CH~-C-COCHCIJNH ~ Cs ll, (t) C N COCHO ~CsHIl (t) HOOC ~ C2Hs --, i ~ i , I I I ' N
., ( Y - 3) C Q
CIH 3 ' >~
CH3-C-COCHCONH ~ C~H',(t) O=C ' `Cl-O CO(CH2)30 ~ C~H " (t) N ~ :
CH 2 ~

' '"
(Y-4) :~

C Q
CH3 ~
CH3-C-COCHCONH ~ C5H,l(t) : O NHCO(CH2) 30 ~ C,H " (t) : ~ ~ I . ; .

`` . .

(Y - 5 ) ~:

C Q C, 2 ~J 2 5 '' C~ CI-C~CIICONII ~NH~I~CH~I ~NIIS~)~C~IID

0 C H 3 :

~ ~ ~ S02 ~ 0-CH2 ~
:`: \~/ :

` : ,'' . .;

,..~
:

~3~2029 ( Y - 6 ) : C Q
CH3 ~
CH3-C-COCHCONH ~ CsHIl(t) O NHCO(CH2)~0 ~ CsHIl(t) NIH

, ~

' (Y - 7 ) OCH~
CIH 3 \~
CH~-C-COCHC09H ~ CsHIl(t) C~Hs ~ CsHIl(t) ~J , ;,'~

~ S 0 2 ~ :~ C ~J , `,"~, ~ OH
1~ ' ' ~'' : ;~
.
"~

- 122 - ~

`:``

~Y--8) C
C H 3 >=~

C N ~ ¦ ~ N H C O C ( C H ~ ) ~
O -C H ~ C H ~-D ~C ~ H ~ I ( t) CsHl~(t) y _ g ) , ,;

.- -C N ~ -Cl-COC HCON N ~ tl NCOC N ~ C N ~ N ~C C

~N \ C~Hs ~ ~

C Q ;;:
.
~ . ~

- 123 - ~:

13~2029 ~ ~

(Y-l O) C Q

CH. I ~ C5H, I (t) ~ NHCO(CH,),O ~C5H" (t) ~ ' ',. .. ;:
COOH . `~ ;~
....
(Y-l 1) .`
C Q
CIH~ ~
CH3-CI-COCHCONH ~ ~) C5H" (t) -`
CH3 ~
~ ~O,NH(CH,)~O ~C5H" (t) .
, ~ ~ (CH2) 30H

1~132029 (Y-l 2) CQ

CH.-CI-COCHCONII

O Q ;

' SO~ '~

CHCOOH
C~ ~ 2 H 2 s ~; , ~; ,.
25 - ~ ~
".':

` 13320~9 ( Y - 1 3 ) ~, "", - ~ .
C Q -:
CIH

CH, j ~ C5H,,(t) 02NH (CH2) 30 ~C~H " (t) ~ :: O=C ~=0 ; : CH2 ~N-CH2 ~3 '~
`:

~;.

13~2029 (Y-l 4) CQ
IH3 >~
CH~ ¦ ~ Csllll(t) O N CD(CH~)30 ~C;H"(t) ' '' ' ' ,.
' SO~

C Q
OH

; ~

`'''' 1332029 ~:

( Y - 1 5 ) CH,-C~-COCHCONH ~ Cl,H- ~ sHll(t _N ~ O H3 CsH~(t) O=C Cl=O

:~ ' " .
( Y - 1 6 ) ~:-: C Q

Cl.-CI-COCHCONH ~ CN

- : O HCOCH-O ~ CsHIl(t) ~ ~ NHSO2CH3 ' ~ ' '.:~

! ; :
~ COOCH3 .:

~. , '' , ~'' (Y-l 7) C
CH~ ~ .
/--\
CH3-C-COCHCONH ~ \ /) CsHIl(t) CH3 1 ~ ~
N ~ N CO(CH~)JO ~ CsH~(t) ~=~O=C Cl=O ~ ''' (Y-1 8) ~ C '" `~
IN~ CH 3 ~ ~, ~ CH3-C-COCHCONH ~ ~ CsH " (t) ~:.
~ h CH
~` ~ N ~ O NHS02(CH~)O ~ C2Hs C Q
c.e ,,, ,'~

133~029 ~ :~

(Y- 1 9) . ~:

C Q ~:

~: CH3-C-~OCHCONH -~
: CH~ ¦ ~ C,~H25 N ~HCOCHO ~ CN ~:
:: O-C `Cl=O ' ~; O - C-CH3 CH3 . :

~, .

.

l33æ~.2~

(Y-2 0) C Q ;
CIH ~
~: CH3-C-COCHCONH ~ ~) C~H9 ~t) C H 3 ~ C, o H 2 ~
O `NHCOC~-O ~ ~OH

SOa ;`

O H ;

.

1 31 ~ ~:
~' `"`' (Y-2 1) C
CH~ ~
CHs~C~COCHCO~H ~ CsHIl(t) I NHCOCHO - ~ C5H " (t) O=C C=O C~Hs C~H~D ~ ~ CH~
: , ~

~.
( Y--2 2 ) . . ::
C Q ~ :~
CH3 ~ ;~
~: ` CH3-C-COCHCONH ~ CsHIl(t) -~

NHCOCHO - ~ CsH~l(t) O=C C;D C~Hs ~ O

CHJ ~ :, :'~

~3~

(Y-2 3) C

CH~-C-COCHCONH

~ ~ ~ . NHSO2C, 6H3 3 ', : ~ ~CQ ~
W ` ~:
S O

C Q
O H

~ .;
: - ~33 - ~-( Y - 2 4 ) :~ NHCCHCH2-SO2 ~: q o ,< d C~2H2~(n) . ; ~
(CH3)3CC-CH-C-NH ~0~ ~;
~ O ~ N ~0 : ~ ~ N I C Q ~ :

`'.
, " .'' ~33202g ~:

(Y-2 5) ;'':
C Q -C H ~
CH3-C-COCHCONH ~ CsHI I (t) O \~ ~ '"
liCO(CH2) 3 -O ~ CsHI I (t) ; ~

~ S02 ;~`~

.i. .;
~' ~,~
~"''' - 1 3 5 ~ ~

1332029 :

In the present invention, 4-equivalent couplers may also be used in combination, if desired. Further, couplers which produce a dye having moderate diffusibility may be used in combination to improve graininess.
Examples of such diffusible dye forming couplers are described in U.S. Patent 4,366,237 and British Patent 2,125,570 as for magenta couplers; and in European Patent ~;96,570 and West German Patent Application (OLS) No. 3,234,533 as for yellow, magenta, and cyan couplers.
;The above-described dye forming couplers and other special couplers may be in the form of a polymer inclusive of a dimer. Typical examples of polymerized dye forming couplers are described in U.S. Patents 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent 2,102,173 and U.S. Patent 4,367,282.
In order to satisfy various characteristic requirements of the light-sensitive materials, two or more different kinds of the couplers described above may be incorporated into one layer, or the coupler of one kind may be incorporated into two or more layers.
A standard amount of the color coupler to be used -.
ranges from 0.001 to 1 mol per mol of light-se~sitive ;silver halide. A preferred amount is from 0.01 to 0.5 mol as to yellow couplers; from 0.003 to 0.3 mol as to magenta .

::

1332~29 couplers; and from 0.002 to 0.3 mol as to cyan couplers, each per mol of silver halide.
The couplers can be incorporated into the light~
sensitive material by various known dispersion methods.
Examples of high-boiling organic solvents to be used in an oil-in-water dispersion method are described, e.g., in U.S. Patent 2,322,027. A latex dispersion method, its effects, and specific examples of latices to be used far impregnation are described in U.S. Patent 4,199,363 and West German Patent Publication Nos. 2,541,174 and 2,541,230. .
The silver halide emulsion to be used in the light-sensitive material may have any halogen composition, such as silver iodobromide, silver bromide, silver chlorobromide, and silver chloride. In the case where color papers or the like photographic materials are subjected to rapid processing or photographic processing ;::
is performed at a low replenishment rate as in the present ~ ' invention, it is preferable to use a silver chlorobromide emulsion or silver chloride emulsion having a silver chloride content of 60 mol ~ or higher, and particularly of from 80 to 100 mol %. `
The individual silver halide grains may have either a ,. -:,.
homogeneous phase or a heterogeneous phase, such as a ~
~`. ,j .i .

core-shell structure or a layered structure having a fused structure, or a combination of these phases.
A mean grain size distribution of the silver halide grains may be either narrow or broad, but it is preferable to use a so-called monodisperse emulsion whose grain size distribution curve has a coefficient of variation ~a quotient obtained by dividing a standard deviation by a mean size, expressed by per cent) within 20%, and particularly within 15%.
In order to obtain desired gradation, two or more monodisperse silver halide emulsions (preferably having the above-recited coefficient of variation) differing in mean grain size can be incorporated into one layer or into separate layers having substantially the same color sensitivity. ~urther, two or more polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be incorporated .
into one layer or separately incorporated into two or more layers.
The silver halide grains may have a regular crystal form, e.g., a cubic form, an octahedral form, a rhombic dodecahedral form, a tetradecahedral form, and a combination thereof; an irregular crystal form, e.g., a spherical form; or a composite form thereof. An emulsion comprising tabular grains, particularly an emulsion - 138 - ~`

comprising tabular grains having an aspect ratio of from 5 to 8 or even more in a proportion of at least 50% based on the projected area of the total grains, can also be used.
An emulsion comprising a mixture of grains having various crystal forms as described above may be used.
The emulsions may be either surface latent image type emulsion wherein a latent image is formed mainly on the surface of grains therein or internal latent image type emulsion wherein a latent image is formed mainly in the :~:,: r interior of grains therein.
The silver halide emulsions to be used can be prepared ;
by known processes as disclosed, e.g., in Research Disclosure, Vol. 176, No. 17643, I, II, and III (Dec., ;
1978). `~
The emulsion to be used in the present invention is usually subjected to physical ripening, chemical ripening, ~-and spectral sensitization. Additives which can be used in these steps and other photographically useful additives which can be used in the present invention are described in Research Disclosure, Vol. 176, ~o. 17643 (Dec., 1979) and ibid, Vol. 187, No. 18716 (Nov., 1979) as tabulated below. ~;

Photo~raphic Additives Kind RD1764~ RD18716 Chemical sensitizer p-23p.648 right column (RC) Sensitivity increasing agent do.
Spectral sensitizer and pp.23-24p.648 RC-p.649 RC
supersensitizer Whitening agent p.24 :~
Antifoggant and stabilizerpp.24-25 p.649 RC
Couplers p.25 ~ :
Organic solvents p.25 Light absorbent, filter dye, pp.25-26 p.649 RC-p.650 and ultraviolet absorbent left column (LC) Stain inhibitor . p.25 RC p.650 LC-RC
Dye image stabilizer p.25 Hardening agent p.26 p.651 LC :~
Binder p.26 do. ;~
Plasticizer and lubricantp.27 p.650 RC
Coating aid and surface pp.26-27 do. ::;
active agent ::
Antistatic agent p.27 . do.

The photographic materiaIs comprise the above~
described emulsion layers provided on a commonly employed flexible support, such as a plastic film (e.g., cellulose nitrate, cellulose acetate, polyethylene terephthalate) ;~

:, ~''~

and paper, or a rigid support, such as glass. For the details of the support and coating technique, Research ~isclosure, Vol. 176, No. 17643, XV (p.27) and XVII (p.28) (Dec., 1978) can be referred to.
In the present invention, a reflective support i~ used advantageously. The reflective support functions to enhance reflecting properties to thereby make a dye image formed on the silver halide emulsion layer clearer. Such a reflective support includes a support coated wi~h a hydrophobic resin having dispersed therein a reflecting substance ~e.g., titanium oxide, zinc oxide, calcium carbonate, calcium sulfate) and a support made of a hydrophobic resin having dispersed therein such a reflecting substance.
The present invention is now illustrated in greater detail by way of the following examples, but it should be understood that the present invention is not deemed to be limited thereto. In the e examples, all the percents and ratios are by weight unless otherwise specified.

,: ~ , . .

A multi-layer color paper having the following layer structure was prepared by coating these layers in the order listed on a paper support having a polyethylene laminate on both sides thereof. The polyethylene layer on :

,~ 1332029 the side to be coated with a 1st layer contained a white pigment (TiO2) and a bluing dye. The resulting sample was designated as Sample A.
The method of preparing the coating compositions was ~;
as follows, taking the composition for the first layer for instance. `
;~ ~'''' PreParation of Coatinq Composition:
To a mixture of 19.1 g of yellow coupler (ExY-2) and 4.4 9 of dye image stabilizer (Cpd-2) were added 27.2 m~
;
u of ethyl acetate and 7.7 nL (8.0 9) of high-boiling organic solvent (Solv-l) to form a solution. The solution was emulsified and dispersed in 185 mu of a 10~ gelatin aqueous solution containing 8 m~ of a 10% sodium dodecylbenzenesulfonate aqueous solution. The resulting dispersion was mixed with emulsions EM7 and EM8, and the gelatin concentra~ion was adjusted so as to have the composition for the first layer. ~;
Each of the 1st to 7th layers further contained a sodium salt of l-oxy-3,5-dichloro-s-triazine as a gelatin hardening agent and Cpd-l as a thickener.

` - 142 -:

LaYer Structure:
: .
1st LaYer tBlue-Sensitive Layer):
Monodisperse silver chlorobromide 0.15 g of Ag/m2 emulsion (EM7) having been spectrally sensitized with sensitizing dye (ExS-l) Monodisperse silver chlorobromide 0.15 g of Ag/m2 emulsion (EM8) having been spectrally sensitized with sensitizing dye (ExS-l) Gelatin 1.86 g/m2 Yellow coupler ~ExY-2) 0.82 g/m2 Dye image stabilizer (Cpd-2)0.19 g/m2 Solvent (Solv-l) 0.35 g/m2 2nd Laver (Color Stain Preventinq Laver): - :
Gelatin o.gg g/m2 Color stain preventing agent (Cpd-3) 0.08 g/m2 3rd LaYer (Green-Sensitive LaYer~:
.
Monodisperse silver chlorobromide 0.12 g of Ag/m2 : ;
emulsion ~EM9) having been spectrally sensitized with sensitizing .
dyes (ExS-2,3) :
Monodisperse silver chlorobromide 0.24 9 of Ag/m2 emulsion (EM10) having been spectrally sensitized with sensitizing dyes ~ExS-2,3) Gelatin 1.24 g/m2 :~
Magenta coupler (ExM-l) 0.39 g/m2 ;
Dye image stabilizer (Cpd-4)0.25 g/m2 :~

~.

Dye image stabilizer ~Cpd-5)0.12 g/m2 Solvent (Solv-2) 0.25 g/m2 4th LaYer (Ultraviolet Absorbin~ Layer):
Gelatin 1.60 g/m2 Ultraviolet absorbent (Cpd-6/Cpd-7/ 0.70 g/m2 Cpd-8=3/2/6) Color stain preventing agent (Cpd-9) 0.05 g/m2 Solvent (Solv-3) 0.42 g/m2 .

5th LaYer (Red-Sensitive Layer):

Monodisperse silver chlorobromide 0.07 g of Ag/m2 emulsion (EMll) having been spectrally sensitized with sensitizing ~
dyes (ExS-4,5) ~:;
Monodisperse silver chlorobromide 0.16 g of ~g/m2 `
emulsion (EMl2) having been spectrally --.
sensitized with sensitizing ~::
dyes (ExS-4,5) Gelatin 0.92 g/m2 ~:~
Cyan coupler (ExC-l) 1.46 g/m2 Dye ima~e stabilizer (Cpd-7/Cpd-8/0.17 g/m2 Cpd-lO=3/4/2~ :
.
Polymer for Dispersion (Cpd-ll)0.14 g/m2 .~:~
Solvent (Solv-l) 0.20 g/m2 ~;~
.~

'.." -':
- 14~ ~

6th Layer (Ultraviolet Absorbinq LayerL;
Gelatin 0.54 g/m2 Ultraviolet absorbent (Cpd-6/Cpd-8/ 0.21 g/m2 Cpd-10=1/5/3) 501vent (Solv-4) 0.08 g/m2 7th LaYer (Protective Layer): -Gelatin 1.33 g/m2 Acryl-modified copolymer of polyvinyl 0.17 g/m2 alcohol (degree of modification: 17%) Liquid paraffin 0.03 g/m2 ;~

In addition, Cpd-12 and Cpd-13 were used as anti-irradiation ~dyes. Each layer furthermore contained A Alkanol XC (a trade name of Du Pont), a sodium alky~benzenesulfonate, a succinic ester, and Magefacx F-120~ a trade name of Dai-Nippon Ink & Chemicals, Inc.) as dispersing agent or coating aid, and Cpd-14 and Cpd-15 as stabilizer for ~ilver halide.
Data of the emulsions used in Sample A are shown in Table 1 below.
i~ :

. ~
1332~29 Emulsion Grain Grain Br Coefficient of No. Form Size ContentVariation*
~m) (mol%) EM7 cubic 1.1 1.0 0.10 EM8 " 0.8 1.0 0.10 -EM9 " 0.45 1.5 0.09 EM10 " 0.34 1.5 0.09 --EMll " 0.45 1.5 0.09 EM12 " 0.34 1.6 0.10 -:

Note: *Standard deviation/mean grain 'size ~;
The compounds used in sample A are as follows.

: ~;: ' . ' ;, ~ " ' ,''.' ;:, '-.~'' - 146 - `~

~: x Y - 2 ( ~ - 2 / ) 13 32 029 ce (C~H3 ) 3CCO(~HCON~/ \~) o ~,N~o NHCo~3C 5 H 1 l (t ) N7LOC2H5 C2Hs I
~H CsHll(t E x M--/

~niC 1 3 H 2 7 CONH~Ce NH /y \
~N~o E x C--/ ( C--/ ) ~ ~:
~ I I , : I . ! ' ; ~ : ~ NHCOCH04~(t)CsHll ~;

CHa ~-(t)CsHll ce ,, ;' ,'`~

~332029 :

~ X S--~

~CH~

ce (CH2)4~03~) (cH2)3 ~03HN(C2H5 ) 3 E x S--2 >--CH =< ~0 (CH2) ~SO~) (CIH2) SO3HN (C2Hs) 3 ~
E x S--3 ~;
0 ' Cl2H5 0 ~,~, ;`'., ¦ l ~CH=C-CH =~
~` ~ ~ N Y ~ \ N1 ~3\~ "~,.~;
(CH2) 2SO~) (CIH2) 2 ~ ~;

S 0 3 H N \~

E x S--4 C H ~<Ç H ~

>--CH =[~L CH =<

. C2Hs I(3 C2Hs - 14 8 ~

E x S--5 ¦' ~/O~,NH~[H ~

N ~N 03H ::
l ~ J ~:

C p d-- 1 ~ ( n =1, 0 0 0 - 1 0, 0 0 0 (Average Molecular ~ ~ Weight = 500,000) C p d--2 HO ~CH~COO {~I--CCH=CH~
~ \ I ..
\(t)C4Hs ~ ~ \ / CH

C p d - 3 OH ~;
CoHI 7 (sec) L 11 ;
(sec) C~H 17 /~
O H

C p d--4 ~: ~
: C3H70 ~ H3 -~;

C~H7~ ~ J l ~ ~ ~ C~H~

3 CH~

C p d - 5 OH CIH3 `:
C ~CH 2 ~COOC6 H, 3 :
: CH3 l CH~ :~
CsHI300C ~ CH 2t~-C / ~ ::~
CH~ OH .-~

, ,' '~".,.

(; p d--6 0~ ~H9 (t) ~ ~.II.(t) C p d--7 N

~H9(t) -C p d--8 O~ 5~Hg (sec) ~, H, (t) C p d--9 OH
~,C9H,7(t) (t)C~H,. /~ ' ~: ` OH

- 151 ~

, ~ ` :'''!"., '; ,' ;'. ,, ' ,, , C p d--10 O~H C.H3~t) ~`

~1, ~
CH2CH2COOC~H, 7 C p d -11 -~-CH2 - IH 3 n ( n =lOO ~1000) CONHC~Hi(t) : C p d -12 H,C200C H - CH = CH - CH =CH COOC2Hs OHO ~ ::

SO~K SO3K :

'. "' : ''~'''' C p d--13 HOOC /~ rCH--CH = CH ~ ~ICOOH

N ~O HO/~N ~
b ~3 SO3K SO~K

C p d~
CH. ~N~
~ . , ,' ~N\N , ~
O H

C p d--15 .
,N HCOlY HCH i, N~

S H

- 1 5 3 - :

Solv-l: Dibutyl phthalate Solv-2: Trioctyl phosphate Solv-3: Trinonyl phosphate Solv-4: Tricresyl phosphate Sample A was exposed to light through an optical wedge and then processed under conditions shown in Table 2 using ~ ;
processing solutions having the following formulations.
The processing was carried on for 75 days at a rate of 2 m2/day (hereinafter referred to as Running Test I) or for 10 days at a rate of 15 m2/day (hereinafter referred ;~
to as Running Test II). :

Processin~ Procedure Amount of Volume SteD TemDerature Time Replenisher of Tank ~::
(C) (sec) (m~/m ) (L) Color Development 35 45 80 or 160 17 :
Blix 30-36 45 215 17 Washing (1) 30-37 30 - lO
Washing (2) 30-37 30 - lO ~;
Washing (3) 30-37 30 250 10 Drying 70-85 60 Note: The washing was effected in a counter-current system from the tank (3) to the tank (1).
; ~
~, , Color Developer A:

Amount ~er 1000 mL
Com~onent Tank S lution ReDlenisher*
Water 800 m~ 800 mL
Ethylenediaminetetraacetic acid 2.0 g 2.0 g 5,6-Dihydroxybenzene-1,2,4- 0.3 g 0.3 g trisulfonic acid Triethanolamine 8.0 g 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g 25 g N-Ethyl-N-(~-methanesulfon- 5.0 g 7.0 g amidoethyl)-3-methyl-4-aminoaniline sulfate ;
Sodium sulfite see Table 3 below Preservakive (see Table 3) 3.03 mol 0.045 mol Brightening agent 2.0 g 2.5 g (4,4'-diaminostilbene type~

Water to make to make lO00 m~ lO00 m~
pH (25C) 10.05 10.45 `~ ' . Note: *Replenishment rate = 160 ml/m2 ", I
~'- ` '~

; , ~.' 1~32~2~

Color Developer B: ~:
~'' ' Amount ~er 1000 mL
Component Tank S~h~_ on ReDlenisher*
Water 800 mc 800 m~ ::
Ethylenediaminetetraacetic acid4.0 g 4.0 g -5,6-Dihydroxybenzene-1,2,4- 0.3 g 0.3 g . ~
trisulfonic acid - :;
Triethanolamine 8.0 g 8.0 g Sodium chloride 1.4 g - :
Potassium carbonate 25 g 25 g ::
N-Ethyl-N-(~-methanesulfon- 5.0 g 9.0 g ~ :
amidoethyl)-3-methyl-4-aminoaniline sulfate Sodium sulfite see Table 3 below Preservative (see Table 3)0.03 mol 0.06 mol Brightening agent 2.0 g 2.5 g (4,4'-diaminostilbene type) :
' Water ~o make to make .
1000 mL 1000 mL . ...
pH (25C) 10.05 10.65 Note: *Replenishment rate = 80 ml/m2 .:
' !: ! . ' , Blix Bath: (The tank solution and the replenisher had the same formulation) Water 400 m~
Ammonium thiosulfate (70%) lOO m~
Sodium sulfite 17 g Ammonium ethylenediaminetetraacetato 55 g ferrate Disodium ethylene diaminetetraacetate 5 g -~laciol acetic acid 8.6 g Water to make lOOO m~
p~ (25C) 5.4 Washinq Water:
Deionized water having a calcium or magnesium content of not more than 3 ppm was used.
Each of the processed sample obtained at the very beginning of the processing and that obtained at the end was determined for their yellow minimum densities, yellow sensitivities, and yellow maximum densities to calculate :~
the respective change (~D~min ~ ~SB ~ and ~D~max ) - The change of sensitivity was expressed in terms of a change of exposure amount which provided a density of 0.6 logE). The results obtained are shown in Table 3.
`': ~ ~: ' ' ' ;

~ '~

. - 157 -. ` ,:
. , ,.

o ~ u~ u~ ~ o o ~ m ~ ~ ~ ~ ~ u~ ~ ~ ~ '.
~,~ E O O ~ ~ O O O O O O O O O . .
V t~i O O O O O O O . O O ;' .~ <I +I+++++. +~I+I++++ '~V _ . . .~ , ~
In m CO `D Irl ~ O t~ J J ~1 C~J J N t~ ) ~1 .C ~1:1 O O O O O O O O O O O O O O O O O
c~ a o o o O o o o o o o o O O o o o o o C~ + I I I ~ I I I + I I + ' ' ' ' ' ' r C .. _ tlO , ~ N ~ ~ ~ ~7 ~ ~ . ~ ~
v E O O O O O O O O O O . O , . . , . .
O C:~ OOOOOOO O O OOOOOO
S <~ + + + + t + + ~ + + + + + + +
-- . .._ ~ O O
E = ~ = - = = c = = = = = = - = = _ o . . _ _~ ~ ' ' ~, C H H ~ ~ H1~ H t--~ ~
:' -- . ~ . . ~' ~: - . -.
.~ .
E~ ~ ~ :' tl~ o ~ In J CO O~
1~ ,~ = = = = _ _ H I = = ~ ~J J S J :
1~ .~
:2: . '' .:

~ ~ r ~ ~ t!- I_ ' 1. 1 ~=~ = ~ I I I I O I I I I O I I O I I I I I
~, u~:~ '' ~

. O ' : "
o ~ C~ m m m m m m m m m m m m m m m m ~ ~

. ~ . .. .~

~ O _ ~ ~ ct~ CS~ O _ ~ co Z . ~

It is obvious from Table 3 that the samples processed with a color developer containing the conventional preservative suffer from a considerable variation of photographic characteristics with the progress of running.
Such a variation is particularly outstandin~ when the samples were processed with Color Developer B which was replenished at a reduced rate (Run Nos. 3 to 7). This tendency is observed irrespective of whether the rate of processing is high (Running Test II) or low (Running Test To the contrary, the variation of photographic characteristics as observed in the comparative run~ can be minimized when processing was carried out at a low replenishment rate according to the present invention.
Difference of processing rate by no means makes the variation larger as can be seen by comparing Run Nos. 8 and 9 or Run Nos. 11 and 12. Further, it was confirmed .
: ~ that better results can be obtained when the color :-~; : developer contains no sulfite ion.

EXAMPhE 2 ~ :. .
:~ Samples B to G were prepared in the same manner as for ;-~
Sample A of Example 1, except for altering the kind of couplers used as indicated in Table 4. ~;

, . .
;
- 159 - ;.
~ '.,'"~

Sample No. Yellow Coupler Magenta Coupler Cyan Coupler .. ____ A Y-21 ExM-l C-l (Example 1) .. . . .

C Y-13 M-45 C-l/C-18 (1:1 by mol) _ . ,':~
E Y-a M-a C-a ~
, : F Y-b M-a C-a ;
. .
G Y-13 M-b C-l/C-18 ~
(1:1 by mol). :

: ~ The couplers shown in Table 4 had the following :
chemical formulae: -Y-a - ,, ' :' ,; ; C~l31 \
CHff{:O~H2~' ') C5Hl 1 ( t ) 3 ~31CO ~ sHll~t) ~;~
I

~- 160 -1332~29 Y-b CH3 ce CH3--C--CO--CH2--CONH~
CH3 ~
NHSO2Cl6H33 ' M-a C2Hs~
t)c5Hll4~ocHooNH ce~
II '~':
c5Hl 1 ~J

~ ,, .
M-b Cl 8 H3 s 0 ~N~

o NH~ ``
N~O "

- ~ ` `,~
~ ; ,C~ "'' ~ `' ~ - 1 6 1 - --~ 1332029 c-a ~CONH ( CH2 ~ ~ ~sHI i('t ) ;

OCH2 CH2 CONHCH2 CH2 (:~CH3 ~''., ~; i Each of Samples A to G was exposed to light through an optical wedge and then processed in the same manner as in Run Nos. 7, 8, or 11 of Example 1. Gradation of yellow (B), magenta (G), and cyan (R) of each of the processed sample obtained in the beginning of the processing and that obtained at the end of the processing were measured, and the respective change was calculated. The gradation is a difference of density between the density of 0.5 and :::
the density at a logE point higher by 0.3 than the logE
providing the density of 0.5 in the D-logE curve. The ~ ~ :
~ -results obtained are shown in Table 5 below.

: ' ~

" ;-",.,," ,~",,"~ ,,"~.,:

1 3~12029 .. -~

o o ce: o o o o o o o c ~ _ + ++ ++ + 5 C ~ N ~ J =t ::
~ ~ ~:1 O C:~ O O O O O :.~
_ o + + + $ 5 5 z s m O O O O sO O g :~
c~ ooo+o~oo~o ~J N N tU S S -- .,:' O O ~ O O O O O O O ,:,:
~11 _1 O O O O O O O ~;
C ~J + + + + + + + ~ .'':',"~
:~ ~ _ . ~ ' .: C: ~. ~1 -- N ~1 S S S
_~ ~:) U O O O O O O O , ~' ~ O O O O O O O
00 O + + ~ + +
. q~ _ ~ .
2 ~ m o ~ o o o o o ,~ $ $ $ $ $ $ $ ,`.',.~1/, _ . `'~'.-~ o ~; $ $ + + + + + : "
~d ~ ~ oo ,~
: ~ ~ 5 5 + + + o :

: ~ ,0 C ~ D
.; _ ,c ~ ooooooo ,-~:, __ $ $ + $ 5 . . ;-~
, 2 _~es m c~ ~ ~ ~ c~ ~; ~
~: ~ ~ ~
'~

. . ~

- 1 6 3 ~
~ - ''. '., , .,...;

-The results of Table 5 reveal that the variation of photographic characteristics (gradation) can be minimized when processing was carried out according to the method of the present invention (Run Nos. 8 and 11). This effect is particularly remarkable in those samples wherein the couplers preferred in the present invention were used (Samples A, B, C and D).

Sample C of Example 2 was imagewise exposed to light and then subjected to continuous processing under conditions shown in Table 6 using processing solutions whose formulations are described below.

-:
Processin~ Procedure Amount of Volume Ste~ Tem~erature TimeReDlenisher of Tank (C) (sec) (mL/m2) (L) Color Development35 45 100 17 Biix ` 30-36 45 215 17 Stabilization (1)30-37 20 ~ :~
Stabilization (2)30-37 20 ~ 10 Stabilization (3)30-37 20 - 10 Stabilization (4)30-37 30 248 10 Drying 70-85 60 Note: The stabilization was effected in a counter- -~: .
current system i rom ( 4 ) to l l ) .

~ .~

~: . ;`'`;
:

'';'',,' "v~

',' - 165 - ..

~ .

Color Developer:

Amount ~er 1000 mL
ComDonent Tank Solution RePlenisher*
Water 800 m, 800 mL :
Benzyl alcohol See Table 7 See Table 7 Potassium bromide " "
Ethylenediamine-N,N,N',N'- 4 g 4 g tetramethylenephosphonic acid Triethanolamine B.0 g 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g .25 g N-Ethyl-N-(~-methanesulfon- 5.0 g 8.0 g amidoethyl)-3-methyl-4-aminoaniline sulfate Preservative (see Table 7) 0.05 mol 0.08 mol Brightening agent 2.0 g 2.5 g (4,4'-diaminostilbene type) Water to make to make 1ooo mL 1ooo mL
~ : pH (25C) 10.05 10.65 ; ~
.:

. ~
;, . , ~

133~029 Blix Bath: (The tank solution and the replenisher had the same formulation) Water 400 nu Ammonium thiosulfate (70%i 100 mu Sodium sulfite 17 g Ammonium ethylenediaminetetraacetato55 g ferrate Disodium ethylene diaminetetraacetate 5 g Water to make 1000 mu pH (25C) 6.00 .
Stabilizinq Bath:(The tank solution and the replenisher had the same formulation) Formalin (37%) 0.1 g , Formalin-sulfurou-qii acid adduct 0.7 g :.
5-Chloro-2-methyl-4-isothiazolin-3-one0.02 g 2-Methyl-4-isothiazolin-3-one 0.01 g ::~
Copper sulfate 0.005 g . ~
Aqueous ammonia (28%) 1.5 nu ;.
! ` ' j ;:
Water to make 1000 mu ~.
pH (25C) 6.7 ''''',~;
The changes of photographic characteristics of magenta during running (~DGmin' ~SG, and ~DGmaX) were obtained in .~ 1332029 the same manner as described in Example 1. The results obtained are shown in Table 7.

',':

:

- 168 - ~

lq X ~ 0 0Cr~ ~1 ~ ~ N N
E ~ . ~ . o o . O
u, a o+ + o+ o+ + 7 + o+ o o _ .
t, ~ ~ t~ J ~ ~ . ~
r; V~ O O O O O O O O O O O
O a o, o, o o, o o, o, + + o+ +
s _ ~
~ C ~ ~ ~ ~ ~ ~ . ~ , v a O O. O. O. O. O O. O. O O. O -~ ~ o+ o + o o+ o+ + o o ':
_ . ~, ~ "~= = C===== ,.
~i O ~ , ,,~.
~ ~' ¦ J ¦ S ~ N

'¢ 2 ':' ~ . ''-'"
~ O~ . ','', ~a ~ s , O , O O , , , , `O
m v~ C ~ ~ ~ o o o o o ~_ 1.~ ; ~ _............. , -o' ~s :, s ~ ~ I I U0~ ~ 0 1 0 1 1 1 1 ' ~ --,,, C .
C~
. . __ C O ~ r m ~ ~ co O~ O -i~ . _ _ '':
- 169 - ;
. . , ~

~332029 It is apparent form Table 7 that the processing method according to the present invention brings about marked improvements on variation of photographic characteristics of magenta (~DGmin~ ~SG, and ~DGmaX)~ This effect is particularly pronounced when the color developer contains substantially no benzyl alcohol and/or a bromine ion as can be seen from the results of Run Nos. ~, 9, ~and 10.

A multi-layer color paper having the following la~er structure was prepared by coating these layers in the order listed on a paper support having a polyethylene laminate on both sides thereof. The polyethylene layer on the side to be coated with a 1st layer contained a white pigment (TiO2) and a bluing dye~
The method of preparing the coating compositions was as follows, taking the composition for the first layer for instance.

Preparation of Coatinq ComPosition:
. To a mixture of 10.~ 9 of yellow coupler (ExY-l), 9.1 g of yellow coupler (ExY-2), and 4.4 9 of dye image stabilizer (Cpd-l) were added 27.2 m~ of ethyl acetate and 7.7 mc (8.0 g) of high-boiling organic solvent (Solv-l) to form a solution. The solutlon was emulsified and ~332029 dispersed in 185 m~ of a 10% gelatin aqueous solutioncontaining 8 m~ of a 10% sodium dodecylbenzenesulfonate aqueous solution. The resulting dispersion was mixed with emulsions EMl and EM2, and the gelatin concentration was adjusted so as to have the composition for the first layer.
Each of the lRt to 7th layers further contained a sodium salt of l-oxy-3,5-dichloro-s-triazine as a gelatin hardening agent and Cpd-2 as a thickener. :

' - 171 ~

... ,. , . . ` . , , , , . . , , , , . , ~ .

Layer Structure:
1st LaYer (Blue-Sensitive LaYer):
Monodisperse silver chlorobromide0.13 g of Ag/m2 emulsion (EMl) having been spectrally sensitized with sensitizing dye (ExS-l) Monodisperse silver chlorobromide0.13 g of Ag/m2 emulsion (EM2) having been spectrally sensitized with sensitizing dye (ExS-l) Gelatin 1.86 g/m2 -Yellow coupler (ExY-l) 0.44 g/m2 Yellow coupler (ExY-2) 0.39 g/m2 ye image stabilizer (Cpd-l)0.19 g/m2 Solvent (Solv-l) 0.35 g/m2 -:
2nd LaYer (Color Stain Preventinq Laver):
: . ~
Gelatin 0.99 g/m2 Color stain preventing agent (Cpd-3) 0.08 g/m2 3rd Laver (Green-Sensitive LaYer~
Monodisperse silver chlorobromideO.OS g of Ag/m~ ::
emulsion (EM3) having been spectrally sensitized with sensitizing dyes (ExS-2,3) Monodisperse silv~r chlorobromide0.11 g of Ag/m2 .
emulsion (EM4) having been spectrally sensitized with sensitizing dyes (ExS-2,3) :~
Gelatin 1.80 g/m2 ~:
Magenta coupler see Table 10 :~.

:

- 172 - ~

,:

~332029 ,.,:, Dye image stabilizer ~Cpd-4) 0.20 g/m2 ~ .
Dye image stabilizer (Cpd-5) 0.02 g/m2 Dye image stabilizer (Cpd-6) 0-03 g/m2 Solvent (Solv-2) 0.12 g/m2 Solvent (Solv-3) 0.25 g/m2 '''~' 4th LaYer (Ultraviolet Absorbinq LaYer):
Gelatin 1.60 g/m2 Ultraviolet absorbent (Cpd-7/Cpd-8/ 0.70 g/m2 Cpd-9=3/2/6) -Color stain preventing agent (Cpd-10) 0.05 g/m2 : :
Solvent (Solv-4) 0.27 g/m2 5th Layer (Red-Sensitive Layer):
~ .
Monodisperse silver chlorobromide 0.07 g of Ag/m emulsion (EM5) having been spectrally ;~
sensitized with sensitizing :
dyes (ExS-4,51 Monodisperse silver chlorobromide 0.16 g of Ag/m2 ~.
emulsion (EM6) having been spectrally sensitized with sensitizing dyes ~ExS-4,5) ~, Gelatin 0.92 g/m2 . .
Cyan coup}er (ExC-l) 0.32~g/m2 ~: Dye image stabilizer (Cpd-8/Cpd-9/ 0.17 g/m2 .
~: Cpd-12=3/4/2) : Polymer for Dispersion (Cpd-ll) 0.28 g/m2 ~i;
Solvent ~Solv-2) 0.20 g/m2 ~.
.~
......

- 173 - ~.
~ .
-,:

6th Layer L~ 9o~lL~9D~C~lO9__aYer)-Gelatin 0.54 g/m2 Ultraviolet absorbent (Cpd-7/Cpd-9/ 0.21 g/m2 Cpd-12=1/5/3) Solvent (Solv-2) 0.08 g/m2 7th Layer (Protective LaYer):
Gelatin 1.33 g/m2 :
Acryl-modified copolymer of polyvinyl 0.17 g/m2 alcohol (degree of modification: 17%) Liquid paraffin 0.03 g/m2 ;

In addition, Cpd-13 and Cpd-14 were used as anti-irradiation dyes. Each layer furthermore contained :~
Alkanol XC (a trade name of Du Pont), a sodium alkylbenzenesulfonate, a succinic ester, and Magefacx F-120 (a trade name of Dai-Nippon Ink & Chemicals, Inc.) as dispersing agent or coating aid, and Cpd-15 and Cpd-16 as stabilizer for silver halide. ~
~: Data of the emulsions used in the sample preparation :~:
are shown in Tab1e 8.

,:

,:,;

- 174 ~

:

Emulsion Grain Br Coefficient of No. Size Content Variation*
(~m) (mol%~
EMl 1.0 80 0.08 EM2 0.75 80 0.07 EM3 0.5 83 0.09 EM4 0.4 ~33 0.10 EM5 0.5 73 0.09 EM6 0.4 73 0.10 .

Note: *Standard deviation/mean grain size . ~
: The compounds used in the sample preparation are as follows. :;

" " ' ';~

~ , :

- 175 - :~

- \

E x Y--1 (CH , ) . CCOCH C O N H

~H C~H~

E x Y - 2 (Y--21) -;~
C ~ , .

(CH,) JCCOCHCO,YH ~

~C C H ~_~c~H~t) q~

~: 0 .' `' - 176 - ~

`` 1332029 E x C--1 (C--11) OH ::
C ~HCOC " H 2 7 (n) C H s C H ~ ~ ~
c .e . . ..
E X S 1 . ~ - . ;

C~ CH~;~Ce (C~l,) .SOJ~
SO~ItN (C,H.), E x S--2 :~ ~ ~D>_ C,H~

(CH,) sSO~) (CIH,) 2 SO,NH (C,H,) 3 :~
'"

'~:

.

~332029 E x S--3 [~ /~CH =<

(CH 2) ~.so~6~ (CH
SOJH ll (C~Hs) ~

E x S--4 . ~:
CH~ cÇH~

N>-- =~NI~
~: C~Hs l ~ C2Hs ` .
E x S--5 ' :~ 3/O\~N~ ~H L

N~N 0~
`~ : l ~ J

~. ~ . .~, ., . . ,.. ,~,,, ,;~ , ,.. ~., 1 7 ~ -,: :

~332029 C p d -=

C p d--2 ~CH7--CH ) n~
~\

(n = 1,000 ~ 10,000) (A~erage Molecular S O 3 K Weight = 500,000) C p d--3 O H `
C.II, (sec) (sec) C~H 17 ~
' 1~ ' 'I l . ~ . ~l .
,, C P d ~ 4 C J H 7 0 ~<~H J

C ~ H 7 0 ~J ¦ 1~O C ~ H 7 C~bC ~ H ~
H J ~:
C p d--5 l2H, C.H.CHCH,OIfO

N ~ :`~

~3\oc ~ (n) C p d--6 ~:~ , C~H" (t) ~,CONH (CH ~) J O ~C S H ~ ~ ( t) NaSO2 ~

--~CONH (CH2) 30 ~CsH I I (t) Csllll(t) '~' ;~

. . .
- 1 8 O - .

133202~

C p d--7 C ~> ~ B . ( t) .H. (t) C p d--8 ~q>
IH,(t) C p d--9 .

~H~(sec) H ~ ( t ) `':

C p d--10 OH
~C o H 1 7 ( t) (t) C.H, 7 /~/
OH
C p d~
~, .
~CH2--IH ~ h 1 n = 100 ~1000) CO~HC~H, (t) C p d--12 0~ C-H-tt) C~

H~CH2COQCoHI7 Solv-l: Dibutyl phthalate Solv-2: Tricresyl phosphate .;
Solv-3: Trioctyl phosphate ~Zi; Solv-4: Trinonyl phosphate '~

~ 3 ~

C p d--13 HOCH, CN . N C ~,~H--CH = C 11--CH = C~ NCH . C H . O H

CH~ CH2 O~INa ~ O~Na C p d ~

I ~H~CH~NC ~ ~ H -Cl =CH ~ I~NCH~CH~OH

CH~ CH2 O~Na ~ O~Na I

1'332029 C p d -- 1 5 `

:
C H 3 _~,N ~N\ `'~
~` N~>
O H ~:;
~ ,'.'";'' C p d -- 1 6 N~N
; H

, _ 184 -; .

.~, 1332o29 The resulting sample was continuously processed under conditions shown in Table 9 below using processing solutions having formulations described below until the total quantity of the color developer replenisher reached twice the volume of the development tank.

Prooessin~ Procedure Amount of Volume SteD TemDerature Time RePlenisherbf Tank :
(C) (sec) (m~/m2) (~) -Color Development 38 100 see Table 10 17 Blix 33 60 150 9 Washing (l) 33 4 Washing (2) 33 20 - 4 : :~
Washing (3) . 33 20 200 4 ::
Drying 80 50 Note: The washing was effected in a counter-current ::
system from the tank (3) to the tank (1).

: , ;., ~ - 185 - ~

~ 332029 , . .

Color Developer:

Amount Der 1000 mL
ComDonent Runnin~ Solution Re~lenisher :
....
Water 800 nL 800 mL
Ethylenediamine-N,N,N',N'- A*: 3.0 g 3.0 g ~-tetramethylenephosphonic acid B**: 3.0 g 3.3 g C***: 3.0 g 3.5 g 1-Hydroxyethylidene-1,1- A*: 2.0 g 2.0 g diphosphonic acid ~-B**: 2.0 g 2.2 g C***: 2.0 g 2.2 g Potassium bromide A*: 0.5 g -*
:
Potassium carbonate 30 g 30 g Brightening agent A*: 1.5 g 2.0 g (WHITEX 4B, a tradename of Sumitomo Chemical Co., Ltd.) B**: 1.5 g 2.4 g `
~- C***: 1.5 g 2.9 g ;~
`~ N,N-Diethylhydroxylamine A*: 4.5 g 5.3 g ~; B**: 4.5 g 6.0 g C***: 4.5 g 6.5 g ,; . , I , , Compound II (see Table 10) A*: 47 mmol 53 mmol `~ B**: 47 mmol 58 mmol C***: 47 mmol63 mmol 3-Methyl-4-amino-N-ethyl- A*: 5.5 g 7.5 g N-(~-methanesul~onamido-ethyl)aniline sulfate B**: 5.6 g 7.9 g - 186 - ~;

C***: 5.9 g 8.3 g Water to make to make 1000 mL 1000 m~
pH t25C) A*: 10.25 10.60 B**: 10.25 10.63 C***: 10.25 10.69 Note: A* : The replenishment rate was 290 mL/m2 B** : The replenishment rate was 120 mL/m2 C***: The replenishment rate was 71 mL/m2 ~,~

'`'~'' .,;.

~: - 187 - --Blix Bath:

~mount per 1000 m~
ComDonent Tank Solution ReDlenisher*
Water 400 mL 400 mL
Ammonium thiosulfate (70~j 200 mL 300 mL
Sodium sulfite 20 g 40 g :.
Ammonium ethylenediamine- 60 g 120 g tetraacetato ferrate :
Di odium ethylenediamine- 5 g lO g ~
tetraacetate ; .
Water to make to make 1000 mL 1000 mL
pH (25C) 6.70 6.30 ;, Washinq Waters (The tank solution and the replenisher had the ~ame formulation) ; Deionized water having a calcium or magnesium content of not more than 3 ppm was used.
:
Each of the samples was exposed to light through an optical wedge and then processed either before and after ; the above-described continuous running to evaluate changes in magenta minimum density (~Dmin) and magenta gradation :
~r) with the progress of running. The gradation is a difference of density between the density of 0.5 and the ~:
density at the logE point higher by 0.3 than the logE :.

- 188 - ~

1~32029 providing the density of 0.5. The results obtained are shown in Table 10 below.

..' ~,'.
' ,~.

~, ' - 189 ~

TABLE l 0 :.

Run Coupler Compound 11 Replenishment Magenta Magenta Remarks 1 M-a _ C +0.06 +0.09Comparison 2 ..Triethanolamine , +0.05 +0.09 ll 3 .l II-26 n +0.05 +0 08 n 4 M-b _ n +0.05 +0 09 II-26 " +0.05 +0.08 ,l 6 M-37 _ A +0.01 i 0 n 7 nTriethanolamine .l +0.01 iO n 8 ll _ B +0.06 +0.06 9 ,-Triethanolamine n +0.06 +0.06 ,l ll _ C +0.09 +0.07 " ;
11 . nTriethanolamine ,l +0.09 +0.06 12 II-26 A :~:O :~:O
13 n n B +0.01 iO Invention .
14 M-42 n .l l0.01 :tO ~ "
M-43 n .l +0.01 iO .l 16 M-37 n C ~0.02 +0 01 ll .
17 M-42 .l n +0.02 +0 01 n 18 M-43 n n +0.02 +0.02 . " i .
. .
19 M-37 n 18 m~tm2* +0.19 +0.09Comparison M-42 l ,l +0.20 +0.09 n 21 M-43 n ,- ~0.18 +0.08 ,l :::
.. .. . . ....
22 M-57 II-27 . B +0.01 +0.01Invention 23 n II-37 n +0.02 +0.01 ,l 24 n II-34 ,l +0.02 +0.01 n n II-28 n +0.02 +0.01 n 26 M-37 II-31 C +0.02 +0.01 27 'l II-34 n +0.02 +0.01 28 _ _ II-28 +0.02 +0.01 . :~ ,.

Note; The processing solution had the same formula~ion as C

~ '~
:: .

.
-- 190 - i~

:r -, ,,: ` .'. . ~

1332~29 M-a tn)C~3Hz7CONH--~--Cl N H -lr N
\ /~
I :~:
Cl~Cl Cl M-b ~ .
G2H .,,`;
(t)HllCs~ HCONl~ N~
- CsHl, (t) CONH~

\N/~O
Cl I Cl Cl - -.:; ~` ~:.. ;:;
`.~ ~ ~ `,`,:

As is apparent from Table 10, in the runs out of the scope of this invention, the photographic characteristics are seriously deteriorated according as the replenishment rate decreases (Run Nos. 6 to 12). According to the construction of the present invention, satisfactory photographic characteristics can be obtained even when the replenishment rate is less than 200 m~/m2 (Run Nos. 13 to .
18 and 22 to 28).
~,, The same color paper as prepared in Example 1 was continuously processed under conditions shown in Table 11 using processing solutions whose formulation are described below until the total quantity of the color developer replenisher reached three times the developer tank.

.

1~32029 Processin~ Procedure Amount of Ste~ T~perature Time ReDlenisher ,.~:
(C) (sec) (m~/m2) :
Color Development 35 45 see Table 12 Blix 35 45 100 ;
Rinsing (1) 30 20 Rinsing (2) 30 20 Rinsing (3) 30 20 200 Drying 70 30 Note: The rinsing was effected in a counter-current system from rinsing (3) to rinsing (1). ~;~

` ~r~. ::: : : , ~,," ~

~ - 193 ~

133~029 Color Developer:

Amount Der 1000 m~
ComDonent Tank Solution RePlenisher Water 800 m~ 800 mL :
Ethylenediamine-N,N,N',N'-A*: 3.0 g 3.5 g tetramethylenephosphonic acid A'**: 3.0 g 3.6 g - B***: 3.0 g 3.7 g ~: C****: 3.0 g 3.9 g Sodium chloride A*: 1.4 g 0.1 g A'**: 1.4 g B***: 1.5 g C 1.7 g Potassium carbonate 30 g 30 g ,~ Brightening ~ A*: 1.6 g 2.0 g ~L agent (WHITEX 4, a trade . name o~ Sumitomo ChemicalA'**: 1.6 g 2.2 g Co., Ltd.) B***: 1.6 g 2.4 g ~ :
~:~ C****: 1.6 g 2.9 g DiethylhydroxylamineA*: 7.0 g 9.1 g A'**: 7.0 g 9.5 g B***: 7.0 g 9.8 g C****: 7.0 g 10.6 g ;~
: Compound II (see Table 11)A*: 47 mmol 53 mmol A'**: 47 mmol 55 mmol : B***: 47 mmol 58 mmol C****: 47 mmol 63 mmol ~h~ 194 - ~

~3.32029 3-Methyl-4-amino-N-ethyl- A*: 5.0 g 7.1 g N-(~-methanesulfonamido-ethyl)aniline sulfate A'**: 5.1 g 7.3 g B***: 5.2 g 7.6 g C****: 5.4 g 8.1 g Water to make to make 1000 mL 1000 m.
pH (25C) A*: 10.10 10.50 A'**: 10.10 10.52 -B***: 10.10 10.53 C****: 10.10 10.59 Note: A* : The color developer replenishment rate was 180 mL/m2 A'** :The color developer replenishment rate was 120 mc/m2 B*** : The color developer replenishment rate was 9 0 mL/m2 -':
; C****: The color developer replenishment rate was 65 mL/m2 Blix Bath: (The tank solution and the replenisher had : ~ the same formulation) Ammonium ethylenediaminetetra- 60 g acetato ferrate dihydrate Disodium ethylenediaminetetra- 4 9 acetate dihydrate ';,'''~''~".

? 1332029 Sodium thiosulfate (70%) 120 nL
Sodium sulfite 16 g Glacial acetic acid 7 9 Water to make 1000 n~
pH (25C) 5-5 Rinsinq Solution:(The tank solution and the replenisher had the same formulation) Disodium ethylenediaminetetra- 0.4 g acetate dihydrate Water to make 1000 m~
pH
- ;
The sample was exposed to light through an optical wedge and processed either before and after the above- : .
described continuous processing. The changes of minimum ~ ;
density and gradation (gamma) with the progress of running were obtained, and the results are shown in Table 12.

~:

- 196 - ~:

13~029 TABLE l 2 _ . _ Run Magenta Compound II Replenishment ~lagenta Magerta Remark~

1 M-a _ A' +0.06 ~0.05Comparison 2 ,lTriethanolamlne ,l +0.06 +0.05,l 3 n II-26 A +0.02 -0.05 n 4 M-37 _ ll -0.02 -0.05 ll ,lTriethanolamine A' +0.08 +0.08 n 6 ll _ ll +0.10 +0.13 7 llTriethanolamine C +0.13 +0.10 ~ _ . ... .. .
8 M-a II-26 A' +0.02 -0.03Invention 9 ,l ,l B l0.02 -0.03 n ll ll C +0.02 -0.04 ll 11 M-37 II-27 A' +0.01 +0.01 n 12 M-37 II-28 B +0.01 +0.01" .
13 M-37 II-29 C +0.02 +0.01 14 M-42 II-30 n +0.01 +0.01,l M-42 II-2 n +0.01 +0.01n 16 M-42 II-13 ,l +0.01 +0.01n 17 M-43 II-31 n +0.01 +0.01n :.
18 M-43 II-34 n +0.01 +0.01. "
. :

The results of Table 12 prove ~hat satisfactory ~`
results can be obtained by following the construction of the present invention (Run Nos. 8 to 18). : :
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various -changes and modifications can be made therein without ~.
departing from the ~pirit and scope thereof.

'''.

. ~.
':
-- 197 ~

Claims (8)

1. A method for continuously processing an imagewise exposed silver halide color photographic material with a color developer containing at least one aromatic primary amine color developing agent, in which said color developer contains at least one compound selected from the group consisting of a compound represented by formula (I):

(I) wherein R1, R2, and R3 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; R4 represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrazino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted amino group; or R3 and R4 are taken together to form a heterocyclic group; X1 represents a divalent group; and n represents 0 or 1, provided that when n is 0, R4 represents an alkyl group, an aryl group, or a heterocyclic group, and a compound represented by formula (II):

(II) wherein R5 represents a substituted alkylene group; and R6, R7, R8, and R9, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and said color developer is replenished at a replenishment rate of from 20 to 120 m? per m2 of the photographic material.

2. A method as claimed in claim 1, wherein said compound represented by formula (I) is present in an amount of from 0.01 to 50 g per liter of the color developer.

3. A method as claimed in claim 1, wherein said compound represented by formula (II) is present in an amount of from 0.1 g to 20 g per liter of the color developer.

4. A method as claimed in claim 1, wherein said photographic material contains at least one magenta coupler represented by formula (III):

(III) wherein R10 represents a hydrogen atom or a substituent; X
represents a hydrogen atom or a group releasable on coupling reaction with an oxidation product of an aromatic primary amine developing agent; Za, Zb, and Zc each represents a methine group, a substituted methine group, =N- or -NH-; one of the Za-Zb bond and Zb-Zc bond is a double bond, with the other being a single bond; when the Zb-zc bond is a carbon-carbon double bond, it may be a part of an aromatic ring; the formula (III) includes a dimer or a higher polymer formed at R10 or X or at Za, Zb or Zc representing a substituted methine group.

5. A method as claimed in claim 1, wherein said color developer contains substantially no bromine or iodine ion.

6. A method as claimed in claim 1, wherein said color developer contains substantially no sulfite ion.

7. A method as claimed in claim 1, wherein said color developer contains substantially no hydroxylamine.

8. A method as claimed in claim 1, wherein said color developer is replenished at a replenishment rate of from 30 to 100 m?/m2.