AU615712B2 - Process of processing silver halide color photographic material - Google Patents

Description

I

i i, w; COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 Form COMPLETE SPECIFICATION FOR OFFICE USE 6 15 7 1 2 Short Title: Int. Cl: Application Number: Lodged: «a o< Complete Specification-Lodged: Accepted: Lapsed: 0 Published: Priority: Related At: Related Art: 0 0 0 o oo e TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: Actual Inventor: S Address for Service: FUJI PHOTO FILM CO., LTD.

No. 210 Nakanuma, Minami Ashigara-Shi, Kanagawa, JAPAN Hideo Miyazaki; Takatoshi Ishikawa; Kazuto Andoh; Hiroshi Fujimoto and Morio Yagihara GRIFFITH HACK CO.

71 YORK STREET SYDNEY NSW 2000

AUSTRALIA

Complete Specification for the invention entitled: PROCESS OF PROCESSING SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL The following statement is a full description of this invention, including the best method of performing it known to me/us:- 6258A:rk ft- 1 4 PROCESS OF PROCESSING SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL FIELD OF THE INVENTION This invention relates to a process of processing silver halide color photographic materials, and more particularly to a processing process for color photographic materials, wherein the stability and the coloring property of a color developer are improved and the increase of the formation of stains in continuous o ood processing is greatly reduced.

o oo 0 BACKGROUND OF THE INVENTION o o0 ooc A color developer containing an aromatic primary O o 0 0 0amine color developing agent has hitherto been mainly o 0 00 used for the formation of color images but the aforesaid color developer is very liable to be oxidized by air or 0 oo metal and it sometimes happens that the oxidation product thereof causes coupling with couplers in color 0,00 o e photographic materials to form dyes or attaches to color photographic materials to cause undesirable stains.

o t ao It is well-known to add various kinds of 0000 o antioxidants (preservatives) to color developers for 00 preventing the occurrence of the oxidation of the color developing agent. However, hydroxylamines which are well-known preservatives and used for various kinds of color developers have such disadvantages that they 4 1* Irreduce the coloring property of couplers and are liable to be decomposed by iron ions or copper ions to form the decomposition products thereof, which are liable to cause fog and give bad influences on the r otographic properties. Thus, these preservatives are not always preferable.

Also sulfite ions are well-known as preservatives and have a function of preventing the formation of fog by decomposing dyes and causing reaction with the oxidation product of a color developing agent but have disadvantages of reducing the coloring property of 00 0o couplers by acting as competing compounds to couplers and causing the reduction of color density by acting as r o V a solvent for silver halide. Thus, sulfite ions are also not preferred preservatives.

For improving the stability of color developers, 0 various investigations of various preservatives and chelating agents have been made. For example, as preservatives, there are proposed aromatic polyhydroxy compounds described in JP-A-52-49828, JP-A-59-160142, o°and JP-A-56-47038 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), and U.S. Patent 3,746,544, hydroxycarbonyl compounds described in U.S. Patent 3,615,503 and British Patent 1,306,176, c-aminocarbonyl compounds described in JP-A- -2- 1 A I 52-143020 and JP-A-53-89425, alkanolamines described in JP-A-54-3532, and metal salts described in JP-A-57-44148 and JP-A-57-53749. Also, as chelating agents, there are proposed aminopolycarboxylic acids described in JP-B-48- 30496 and JP-B-44-30232 (the term "JP-B" as used herein means an "examined published Japanese patent application"), organic phosphonic acids described in JP-A-56- 97347, JP-B-56-39359,and West German Patent 2,225,639, phosphonocarboxylic acids described in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-126241 and JP-Aooo 55-65956, and the compounds described in JP-A-58-195845 So o and JP-A-58-203440, and JP-B-53-40900.

oO However, by the use of these compounds, o sufficient preservativity is not obtained and also the prevention of the occurrence of stains at continuous S'processing or after processing and the improvement of the stability of processing solutions, which are the objects of this invention, have not been sufficiently obtained.

o00o Also, in processing of silver halide color photographic materials, shortening of the processing steps and processing time is becoming a very important technical theme since it greatly contributes to the promotion of mini processing laboratories for color photographic materials or shortening of the time for -3- .1 1 1 delivery of finished products as well as the reduction of the size of an automatic processor.

For silver halide color photographic materials, various kinds of dyes are used for the purposes of preventing irradiation at image exposure or at printing, or increasing the stability to so-called safelight without reducing the sensitivity, reducing the latent image sterage stability, giving bad influences on the photographic properties, and reducing the quality of o images by causing stains (color residue) after processing.

However, when in quick processing, washing is Sinsufficient or these dyes are dissolved 'in a color developer, wash water, and/or a stabilization solution, the processing solutions are colored or even the processed color photographic materials are colored to form undesirable stains as the case may be. These oo o o phenomena are serious problems in, particularly, quick processing.

otoo, For preventing the occurrence of stains (stains at background portions) caused by such dyes, it is preferred to use dyes which become colorless dyes by being decomposed by alkali or reducing agent in a color developer but it frequently happens that the decomposition is insufficient to cause undesirable color -4 stains and thus sufficiently satisfactory techniques of overcoming the aforesaid problems have not yet been found.

SUMMARY OF THE INVENTION A first object of this invention is, therefore, to provide a process of processing silver halide color photographic materials excellent in the stability of the color developer being used.

A second object of this invention is to provide Sa process of processing silver halide color photographic materials giving greatly reduced formation of stains at o° continuous processing.

o~o o A third object of this invention is to provide a process of processing silver halide color photographic materials giving less stains after processing the color photographic materials even in quick processing.

S0 It has now been discovered that the aforesaid ooo o0 objects can be effectively attained by the process of this invention as described herein below.

0. 0 That is, according to this invention, there is o provided a process of processing a silver halide color 0 photographic material, which comprises processing, after imagewise exposure, a silver halide color photographic material with a color developer containing an aromatic i primary amine color developing agent, at least one of A ii- 1 r i i I- 1 hydrazines and hydrazides each represented by following formula and at least one selected from monoamines represented by following formula (II) and condensed ring type amines represented by following formula (II R N(I)3

R

2 N X1) nR4 wherein Ri, R 2 and R3 each represents a hydrogen atom, S. an alkyl group, an aryl group, or a heterocyclic group; 0 4a o R4 represents a hydrogen atom, a hydroxyl group, a Shydrazino group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a

Q

So carbamoyl group, or an amino group; X1 represents a divalent group; n represents 0 or 1, provided that when S n is 0, R4 represents an alkyl group, an aryl group, or fo o a heterocyclic group; and RI and R 2 or R3 and R4 may form oo together a heterocyolic ring; R6 *boo R 5

-N-R

7

(II)

0 wherein RS, R6 and R 7 each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group; and RS and R 6 R5 and R 7 6l or R6 and R 7 may combine with each other to form a nitrogen-containing heterocyclic ring; and

R

8 N X 2

R

9

(III)

0 0 0 oa 0o a 0 33 O 3 0 i wherein X2 represents a trivalent atomic group necessary for completing a condensed ring; and R8 and R 9 which may be the same or different, each represents an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

Furthermore, in this invention, the formation of stains in quick processing or continuous processing with quick processing can be more effectively prevented by carrying out the aforesaid processing in the presence of at least one kind of compounds represented by following formula (IV) or by carrying out the aforesaid processing using a silver halide color photographic material containing at least one kind of compounds represented by following formula (V)

Z-S-M

(IV)

7 wherein M represents a hydrogen atom, a cation, or -S-Z; and Z represents a heterocyclic residue containing at least one nitrogen atom; and R21 0 LtL

R

22 N N 0 HO N

(V)

1

(R

23 -CH)m

(R

24

-CH)

2

(Q

1 tltX 4 tCH 2 )p 1

(Q

2 t2tX 5 tCH 2 p-Y2) 2 wherein R 21 and R 22 each represents -COOR25, o

I

R

26

-COR

2 5 (wherein R25 and R26 each represents a hydrogen o atom, an alkyl group, or an aryl group), or -CN; R23 and R24 each represents a hydrogen atom or an alkyl group; Q1 oo and Q 2 each represents an aryl group; X4 and X5 each represents a bond or a divalent linkage group; yi and y2 each represents a sulfo group or a carboxyl group; L1, L2, and L 3 each represents a methine group; mi and m2 each represents 0, 1, or 2; n represents 0, 1 or 2; pi and P2 each represents 0, 1, 2, 3, or 4; si and s2 each represents 1 or 2; and tl and t 2 each represents 0 or 1, with, however, the exclusion of the cases that mi, pi, and ti are simultaneously 0 and that m2, P2, and tb are simultaneously 0.

8 DETAILED DESCRIPTION OF THE INVENTION Then, the invention is explained in detail.

First, the compounds for use in this invention are described below in detail.

The compounds of formula for use in this invention, that is, hydrazine analogues composed of hydrazines and hydrazides are explained.

In formula R 1

R

2 and R 3 each, independently, represents a hydrogen atomk a substituted or unsubstituted alkyl group (preferably having from 1 to 0 carbon atoms, methyl, ethyl, sulfopropyl, 0 0 0 .o carboxybutyl, hydroxyethyl, cyclohexyl, benzyl, Son 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), or a substituted or unsubstituted heterocyclic group (preferably having from 1 to 20 carbon atoms, more preferably a 5- or 6-membered ring having at least one of oxygen, nitrogen, sulfur, etc., as hetero atom, e.g., pyrydin-4-yl, N-acetylpiperidin-4-yl).

In formula R 4 represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrazino group hydrazino, methylhydrazino, phenylhydrazino), a substituted or unsubstituted alkyl group (preferably having from 1 to 20 carbon atoms, e.g., 4 -9k# I -rul- 1 methyl, ethyl, sulfopropyl, carboxybutyl, hydroxyethyl, 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 unsubstituted heterocyclic group (preferably having from 1 to carbon atoms, more preferably a 5- or 6-membered ring having at least one of oxygen, nitrogen, and sulfur as hetero atom, pyridin-4-yl, imidazolyl), a substituted or unsubstituted alkoxy group (preferably 000 00 having from 1 to 20 carbon atoms, methoxy, ethoxy, methoxyethoxy, benzyloxy, cyclohexyloxy, 6ctyloxy), a substituted or unsubstituted aryloxy group (preferably having from 6 to 20 carbon atoms, phenoxy, pmethoxyphenoxy, p-carboxyphenyl, p-sulfophenoxy), a substituted or unsubstituted carbamoyl group (preferably having from 1 to 20 carbon atoms, unsubstituted carbamoyl, N,N-diethylcarbamoyl, phenylcarbamoyl), or a substituted or unsubstituted amino group (preferably having from 0 to 20 carbon atoms, amino, hydroxyamino, methylamino, hexylamino, methoxyethylamino, carboxyethylamino, sulfoethylamino, N-phenylamino, psulfophenylamino).

When the groups shown by Rl, R2, R3, and R 4 have a substituent, preferred examples of the substituent are 10

F'

halogen atoms chlorine, bromine), a hydroxyl group, a carboxyl group, a sulfo group, an amino group, an alkoxy group, an amido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a nitro group, a cyano group, a sulfonyl group, and a sulfinyl group, and these groups each may further have a substituent.

Also, in formula X1 is preferably a

NH

1 divalent organic residue, such as -SO 2 and o0o and n is 0 or 1. However, when n is 0, R 4 represents a ooo group selected from a substituted or unsubstituted alkyl 0 (0 group, a substituted or unsubstituted aryl group, and a o .o substituted or unsubstituted heterocyclic group. RI and

R

2 or R3 and R 4 may form together a heterocyclic group.

When n is 0, it is preferred that at least one of R1 to R4 is a substituted or unsubstituted alkyl group o and it is more preferably that R1, R2, R3, and R 4 are a hydrogen atom or a substituted or unsubstituted alkyl group (with, however, the exclusion of the case that Ri, o R2, R3, and R 4 are simultaneously a hydrogen atom). In this case, it is particularly preferred that Ri, R 2 and

R

3 are a hydrogen atom and R4 is a substituted or unsubstituted alkyl group; R1 and R3 are a hydrogen atom 11 L o 0i ourr and R 2 and R 4 are a substituted or unsubstituted alkyl group; or R1 and R 2 are a hydrogen atom and R3 and R4 are a substituted or unsubstituted alkyl group (in this case R3 and R4 may form together a heterocyclic ring).

When n is 1, X1 is preferably R 4 is preferably a substituted or unsubstituted amino group, and R1 to R3 are a hydrogen atom or a substituted or unsubstituted alkyl group.

In formula n is more preferably 0.

The alkyl group shown by Ri to R 4 has preferably from 1 to 10 carbon atoms, more preferably from 1 to 7 carbon atoms. Also, preferred examples of the substituent for the substituted alkyl gzoup are a hydroxyl group, a carboxylic acid group, a sulfo group, and a phosphonic acid group. When two or more substituents exist, they may be the same or different.

The compound shown by formula may form a tris compound or a polymer bonded at Ri, R 2 R3, or R4.

Then, specific examples of the compound shown by formula are illustrated below but the invention is not limited to them.

12

U,

(I-i)

CH

3 NNH 2

CH

3 (1-2)

CH-

3

NHNHCH

3 (1-3) 0 0 00 Of~ 0 0 0 0 00 00 41 0 00 00 0 o o 0000 0 IIC 0 0 0 0 00 00 41 0 0 0 ~0 0 0 0 0 0 0 0

HOC

2

H

4 H0C 2

H

4

NNH

2 (1-4)

N_NHNH

2 i 1) 0~

NH

2 NI- la NHNH 2

CNH

'I 0 0 0 (1-6) 13 The following statement is a full, description of this invention, including the best method of performing it known to me/us:- 62 58A: rk ~I4 0 (1-7) NHN

CH

2

COOH

NHN"CH

2

COOH

(1-8)

HOOCCH

2

NHNHCH

2

COOH

(1-9)

NH

2 NH-tCH 2 -3-NHNH 2 o cici ci 00 ci'; ci ~ci ci 0 0 00 ci a';

NH

2

NHCH

2

CH

2 0H (I-11)

OH

7

'I

(1-12)

NII

2 NH- (CE 2 3

-SO

3

H

a i C (1-13)

NH

2 NH- H 2 4

-SO

3

H

14 (I-14j

NH

2 NH- (CH 2 3

-COOH

(1-15) HOOC CH 2

NHNHCH

2

COOH

0 00 C, 0 0 00 0 00 0 00 00 C. 0 C 00 0 "0 CO 0 0 0 C- 0) (1-16)

"(CH

2 j-COONa

NHN">CH

2 t2-COONa (1-17) 0~'n 0 00 0 000 00 (1-18) o 0 C) 01 0 0

CH

2

NHNH

2

SO

3 Na NaOOCCHNHNHCHCOONa I I

CH

3 Ut1 3 15 (1-19)

NH

2

NHCH

2

CH

2 COONa (1-20)

NH

2

NHCH

2 COONa 00 0 00 0 no 0 0~ 0 (1-21) H2NNHCH2CH 2

SO

3 Na (1-22) J 1" u a C4H9 (n) Hl 2 NNhCHCOOH

C

6

H

13 (n) n 2 NNhCHCOOH 00$?0 00 (1-23) 0 16 (1-24)

C

4 H9 (n)

H

2 nN--CHCOOH) 2 (1-25) 11 2 NN-t-CH 2

CH

2

SQ

3 Na) 2 0 0 0 00 0 0 0 0 ~s 0 1 0 00 (1-26) H2NN-tCH 2

CH

2

CH

2

SO

3 Na) 2 (1-27)

C

2

H

H

2 N(CHCOOH) 2 0 (1-28)

CH

3

H

2

NNHCHCOOH

00 0 17 j 1-29) H2NN

CH

2

CH

2 0H

H

2 N CH2COOH (1-30)

H

2

NNHCH

2

CH

2 NI, 'H3

'CH

3 0 Q 00 0 00 0 tto 0 0 0 00. 0 o t.0 0 0 0 to 0~ 0 00 0 to 0 0 0 (1-31)

CH

3 11-32) -tCH2-N-CH2CH 2 1-

NH

2 (average molecular weight is about 4,000) 18 (1-33) -tCH 2 -CHt X -tCH2-CHI

COON

NHNH

2 (average molecular weight is about 20,000) 0 0~ 00~ 9 0 .0 0" 0 00 C. ~c,

C.

0 0 0 0

C.

C.

C.

0 00 00 0 o 00 Oc.OU 00 (1-34)

NH

2

NHCONH

2 (1-35)

NH

NH

2

NHCNH

2 (1-36) a. 00C

NH

2 NHCONH NH 2 19

I

(1-37)-

NH

2 NHS0 3

H

(1-38)-

NH

2 NHS0 2

NHNH

2 0 0 (1-39) (1-40) #00 0# 0 S 00

I

o (1-41)

CH

3

NHNHSO

2 NHNHCH3

NH

2 NHCQNH- (CE 2 3 -NHCON~j.H2

NH

2

NHSO

2 NH NHSO 2

NHNH

2 20

J

"I

I

(1-42)

NH

2

NHCOCONHNH

2 (1-43)

NH

2 COCONHNH UQI 0 0

LI

9 06 6 oo 0 0 0 9 0 0 C LI O jo 1 0 LI 9 LO LI

LI

U

0 0 LI 0 LI U (1-44) F\-MCONHNHi 2 (1-45)

NH

2 NHCO CONINH2 (1-46)- U 00

U

13 .0

I

NH

2

COCONHNH

2 21 LI-47).

CH

3 0 L£ 8) Hooc- Nnwnin \OO CN-H Uft~ 4,~ 4 .00 (1-49) 0 HO3S NCHH 4 I

CO

U

0 112NS03 F\,NHCNHNH 2 (1-51) 22 (1-52) HOOC 0

HOOC

(1-53) 4 0 4

V

3 0 NaO 3 S Nn;CVNn 2 0 NaO 3 S /\NHC."Nn 2 (I-54)~ (1-55) H13 0

NCNHNHNH

23

A~.

(1-56) n 2 NNI-C NnuNnNr 2 (1-57).

0 0 11 11

H

2 NNHCNRH- (CR2) 6

-NHCNHNH

2

CR

3 N-CNHNH 2

CH

3 0

HOOCCH

2

NCHR

HOOCCH

2 (1-60)- 0 11 Na03 SCI 2

CH

2

NHCNHNH

2

C

24 (1-61) 0

HOOCCH

2

CH-

2

NHCNHNH

2 (1-62) 0 S0 3 Na 444~ 4 4 0 I 9 It (1-63)

NH

2

NHCOOC

2

H

(1-64) 41 0 0 4 II,

I

#44

I

(1-65)

NH-

2

NHCOCH

3

NH

2 NHCO HO1 25 (1-66

NH

2

NHSO

2

CI.

3 (1-67)

NH

2

NHCH

2

PO

3

H

2 CC 0I C 1 0 (1-68) N9 2 .L-6§91 C C C

NH

2 I4HCO CONHNH 2 (1-70) Q -CONH-NH 2 26 (1-71) HOOC CO-NHNH 2 (1-72) NaO3S CONHNH2 o 4 0 0 0 0 0 0 0 4 4 0 0 ~4 0 0 0 0 (1 -73)

(CH

3 3

CCONHNH

2 I-74 0 11

(CE

3 3 COCNHNE2 (1-75) MM-1-CONHNH2 27 (1-76) iN CNEH (1-77)

(CH

3 2 N CONHNH 2 0 o 0 (1-78)

CONHNH

2

CH

2

COOH

(1-79) N 'CONHINH2 (1-80)

HOCII

2

CH

2

SO

2

NHNH

2 28 Ioc -(18-1 NaO 3

SCH

2

CH

2

CONHNS

2

E

2

NCONHCH

2

SO

2

NHNH

2 0 000006 00 0 00 0 0 04 0 0 o 0 0 06 0 0 0 0 0 0 Hooc

SO

2

NHNH

2

HOOC

-;8Z4)

-,CH

2 p0 3 11 2 11 2 NN HP0 H2 (1-85) 1i 2 NNHCHi 2 CH2P0 3 H2

OH

tCH2NC"2%CH4--

NH

2 to 100) 29 0 0 0 0 C 0 "1 o a 0 00 oo o <o 0 (0 0 00o 4 0 €<0 o o S 0 0 O* 0 0 0 i o 0 Other specific examples of the compounds shown by formula are described in JP-A-63-146041, JP-A-63- 170642, JP-A-63-146042, JP-A-63-170643, and JP-A-63- 146043.

Many of the compounds shown by formula are commercially available and also can be synthesized according to the methods described in Organic Syntheses, Coll., Vol. 2, pages 208 to 213, Journal of American Chemical Society, 36, 1747 (1914), Yukaqaku (Oil Chemistry), 24, 31 (1975), Journal of Organic Chemistry, 25, 44 (1960), Yakuqaku Zasshi (Journal of Pharmacology), 91, 1127 (1971), Organic Syntheses, Coll. Vol.

1, page 450, Shin Jikken Kaqaku Kooza (New Experimental Chemistry Course), Vol. 14, III, pages 1621 to 1628 (published by Maruzen), Beil., 2, 559, ibid., 3, 117, E.B. Mohr et al, Inorganic Syntheses, 4, 32 (1953), F.J.

Wilson and E.C. Pickering, Journal of Chemical Society, 123, 394 (1923), N.J. Leonard and J.H. Boyer, Journal of Organic Chemistry, 15, 42 (1950), Organic Syntheses, Coll., Vol. 5, page 1055, P.A.S. Smith, Derivatives of Hydrazine and Other Hydronitrogens Having n-n Bonds, pages 120 to 124 and pages 130 to 131 published by the Benjamin/Cummings Publishing Company, 1983, and Stanley R. Sandler and Wolf Karo, Organic Functional Group Preparations, Vol. 1, 2nd Edition, 457 (1968).

30

I

The addition amount of the hydrazine or hydrazide shown by formula is from 0.01 g to 50 g, preferably from 0.1 g to 30 g, and more preferably from g to 10 g per liter of color developer.

The monoamines for use in this invention are the compounds shown by formula (II)

R

6

I

R5-N-R7

(II)

o oooo wherein R 5 R6, and R 7 each represents a hydrogen atom, 0 QC% an alkyl group, an alkenyl group, an aryl group, an o" aralkyl group, or a heterocyclic group; and R 5 and R 6 R5 and R 7 or R 6 and R 7 may form together a nitrogencontaining heterocyclic ring, ,;The groups shown by R 5 R6, and R7 may have a substituent and as the substituent, there are a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom, a nitro group, an amino group, etc. R 5

R

6 and R7 are particularly preferably a hydrogen atom or an alkyl group.

Specific examples of the compounds shown by formula (II) are shown below but the invention is not limited to them.

31 hi-i NtCH2CH2OH)3 11-2

H

2

NCII

2

CH

2 0H *0000 ft 0 ft 00 0 0 Oft #0 0 *,O0 00 4 Oft ft ft 0 ft 40 000 ft ft 0 '04 ft ft ft~ 11-3 HNtCH 2 CH-20H)2 11-4

OH

C

7

H

3 5 NTCHl 2 CHCH2OH) 2 11-5 9-j

-CH

2

-CH

2

QH

32 11-6 r: NCH 2

CH

2 0H 11-7

CH

3 -lk__NCH 2

CH

2

OH

o CO ~oUo 000 0 0 11-8 HO NtCH2CH2QH)2 11-9

CH

3 C/1 1 CH1 2

-H

2

H

11-10 (HOCH2CH2)-2-NCH 2

CH

2

SO

2

CH

3 33 11-11 H~j-CH 2

COQH)

2 11-12

HOOCCH

2

CH

2

CHCOOH

NH

2 0 (1 0 o 0 0000 o 00 o 00 00 0 0 0 0 00 0 0 11-13

H

2

NCH

2

CH

2

SO

2

HN

2 11-14

C

2 HS

N-CH

2

CII

2 00H 2

CH

2

OH

H2N-CltCH 2

OH)

3 34 I-i 11-16

HOCH

2

CRCOOH

NH2 11-17 2-NjCH 2

CH

2

OH)

2 OCH3 11-18 c> -CH 2

NH

2 11-19 F CH 2

-NCH

2 CfI 2

OH

11-20 Trhe aforesaid compounds of formula (11) are mostly commercially available.

w The condensed ring type amines for use in this invention are the compounds shown by formula (III)

R

8 N

X

2 (1II)

R

wherein X2 represents a 'i.valent atomic group necessary for completing a condensed ring; and R 8 and R 9 which o may be the same or different, each represents an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

In the amines shown by formula (III), the compounds shown by following formula and are particularly preferred.

R

10 0 N R--X 3 (1-a)

R

1 2 wherein X3 represents -N or -CH, Ri0 and Rll have the same meanings as RO and R 9 in the aforesaid formula (III) and 0

II

Ri 2 represents the group shown by Rio and RII or -CH 2

C-.

36 ti In formula X3 is preferably -N and the carbon atom number of the group shown by Ri 0 R11, or R 12 is preferably 6 or less, more preferably 3 or less, and most preferably 2.

RIo, R11, and R12 are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

SR

13 SN (l-b)

N

R

1 4 wherein R1 3 and R14 have the same meanings as R 8 and R 9 in the aforesaid dormula (III).

In the compounds shown by formulae and (1the compounds shown by formula are particularly preferred.

Then, specific examples of the compounds shown by formula (III) described above are illustrated below but the invention is not limited to them.

37 ii- -r iii-'

(N,

111-2 0 111-3 0 0 0 111.-4

N

111-5

CH

2 0H OH 38

A

111-6 CTI4:::N 111-7

CH

3 N N 4 4' 4 0 04 4 0g0~ 4 0 0 44 04 0 4 4 44 111-8

CH

3

CE

3 111-9

NE

0 ~'4 0 0 K, U 0 111-10 Cr

N

39 -26- IIi

OH

111-12 rN 000 0 111-13 00 .000 0 00 111-14 N N 40 a A I11-16 III-17 S1 III-18 The compounds of formula (III) are mostly easily commercially available and also can be synthesized according to the methods described in Khim. Geterotsikl.

Soedin., 272-275 (1976), ibid., 1123-1126 (1976), U.S. Patents 3,297,701, 3,375,252, and S4,092,316.

The addition amount of the compounds shown by formulae (II) and (III) is from 0.1 g to 50 g, 41 L s ~~r#rl preferfably from 0.5 g to 20 g per liter of color developer.

Then, the compounds shown by formula (IV) described above are explained in detail.

The heterocyclic residue shown by Z in formula (IV) may be condensed and specific examples of the preferred compound are imidazole, triazole tetrazole, thiazole, oxazole, selenazole, benzimidazole, benzoxazole, benzthiazole, thiadiazole, oxadiazole, benzselenazole, pyrazole, pyrimidine, triazine, pyridine, naphthothiazole, naphthimidazole, naphthoxazole, azabenzimidazole, purine, and azaindenes triazaindene, tetraazaindene, pentaazaindene).

The heterocyclic residue and the condensed ring thereof may be substituted, Examples of the substituent are an alkyl group methyl, ethyl, hydroxyethyl, trifluoromethyl, sulfo- Spropyl, dipropylaminoethyl, adamantane), an alkenyl group allyl), an aralkyl group benzyl, pchlorophenethyl), an aryl. group phenyl, naphthyl, p-carboxyphenyl, 3, 5-di-carboxyphenyl, m-sulfophenyl, pacetamidophenyl, 3-capramidophenyl, p-sulfamoylphenyl, 0"*0m-hydroxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, 2methoxypheny.), a heterocyclic residue pyridine, furan, thiphene), a halogen atom chlorine, -42- Si, bromine), a mercapto group, a cyano group, a carboxyl group, a sulfo group, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an amino group, a nitro group, an alkoxy group methoxy), an aryloxy group phenoxy), an acyl group acetyl), an acylamino group acetylamino, capramido, methylsulfonylamino), a substituted amino group diethylamino, hydroxyamino), an alkylthio or arylthio group methylthio, carboxyethylthio, rulfobutylthio), an alkoxycarbonyl group methoxycarbonyl), and an S° aryloxycarbonyl group phenoxycarbonyl).

SIt is necessary that the heterocyclic residue shown by Z in formula (IV) contains at least one S nitrogen atom but the heterocyclic residue contains preferably at least 2 nitrogen atoms, more preferably at .y least 3 carbon atoms, and particularly preferably at least 4 carbon atoms.

Specific examples of the preferred mercapto type compounds shown by formula (IV) are illustrated below but the invention is not limited to these compounds.

43 I i i 4/ IV H H Cv=C

HCC---C-SH

H H IV .2) (n)C 4 i 9 -N-C-SNa

I

NzwN, 3) 03, H H

C=C

C_

H

H HI (IV 4 H H /C C-N--C-SE

NN~

NEC 0 (Iv 3 33 0 H H

C=C

NaO 3 S-C

C-SH

c N, J4 H H 44 IV -z IV 7) 000 00 00 0000

HEH

C=C

c

N\

OH NN

HEH

C=C

H-d C-SH H H '/N"N

CE

3

H

3 c-N C-SE

CE

3 HE H IV- 0 1 1 (IV F 0 u c (IV- 0 .1 3 C-N- C-SE I it CHi 3 CO.NH-Ck c,

H

45 f (IV

H

HC c C NH 11C CNSH

H

(IV 2 0 0 'I 0 0 011 11 0 11 0 0 0 5 EC 'C--Nmi

H

H CH-ICH 2

OH

C c I HC SH

H

(IV 3 Na3S C-NHsl I q I ki i 46

LK--

IV-

Iv- )NHCQCHi 3 HC% ,C-SH

H

HCc~ SH

H

I V- )H

HOO

2 9

C-SH

H2C C%N'kC-SH

H

2 7 zo)S0 2 -NH{ H

H

3

INCC~C

H6jC.,CC SH

H

.47- (IV .2

H

(IV-.2 .2 02H HC~lc0.c SH

H

HNO

2 ,CW1-

H

HC d- 0 CH.~

HH

(IV~4 IV- 2 s H H H H (IV- .z 2

N-N

(IV- .2 7) HS SCH3 IV- .2

NN-

M-IOO~

(CH

2 4

SO

3 N~a 49 (IV -3 0 H H

C=C

N-N HC~ //C1

H

IV 3 C-6'

N-

C C H c-

HH

(Iv- 3)

OR

SH

(IV -3 44 (IV -3 Ii uCH I I

SH

01C SH -N C Cit

I

(IV 3 6 (:CV 3 7 *53 Nolu.C- NH I I c 'Y N 66

IV_

HC N CHa

SH

N

2 'i-N 4 E c N OH1 3 (IV 44

CH

3 kiC':c IN'NCH IV v- 44 3

CH

3

NCONC-N

I I I

SH

IV 44 44

CH

3 I V 4J

NHCNHCH

3 -53 At (IV-46)

N-N

N N &N

NHCCH

3 (IV-47) 0 C C-SH

H

3

CQC-N

In the compounds shown by formula (IV), particularly preferred compounds are compounds IV-27, IV-46, and IV-47.

The compound showr by formula (IV) for use in this invention may exist in a silver halide color photographic material and/or a color developer and particularly preferably exists in a silver halide color photographic material.

Also, the coinpouids shown by formula (IV) may be used singly or as a mixture LhereonE.

54 When the compound shown by formula (IV) exists in a silver halide color photographic material, the compound may exist in any layer of the photographic material and further may exist in two or more layers.

Also, the amount of the compound shown by formula (IV) is in the range of preferably from 10-7 mol to 10-1 mol, more preferably from 10-5 mol to 10-2 mol per mol of the silver halide in the layer containing the compound.

When the compound shown by formula (IV) exists in a color developer, the amount of the compound is preferably from 10-10 mol to 10-3 mol, more preferably from 10-10 mol to 10-4 mol per liter of the. color developer.

The processing process of this invention, which is carried out in the presence of the compound shown by ,o formula is par',icularly effectively applied to a ,silver halide colov photographic material having at S least one silver halide emulsion layer containing a silver halide substantially composed of silver chloride The term "substantially composed of silver chloride" as used throughout the description and claims means that 80% or more, preferably 95% or nore, 4 and more proferably 98% or more of the silver halide is silver chloride.

w| o, S From the standpoint of prevention of the reduction o. sonsit ivity,, it is preoerred that no more than 99.8% of the silver halide is silver chloride, Then, the ccmpour.ds shcwn by fornzla are e<plaind in detail.

r 5

S

In formula R21 and R 22 each, independently, represents -COOR 2 5 -CON-R2 5

-COR

25 or -CN [wherein

R

2 6

R

25 and R 2 6 each represents a hydrogen atom, an alkyl group or substituted alkyl group methyl, ethyl, butyl, hydroxyethyl, phenethyl), or an aryl group or substituted aryl group phenyl, hydroxyphenyl)]; and R 23 and R 24 each represents a hydrogen atom or an alkyl group or substituted alkyl group methyl, ethyl, butyl, hydroxyethyl).

In formula Q1 and Q 2 each represents an aryl group phenyl, naphthyl); X4 and X5 each represents a bond or a divalent linkage group; Y 1 and y2 each represents a sulfo group or a carboxyl group; L1, L2, and L 3 each represents a methine group; mi and m2 each represents 0, 1 or 2; n represents 0, 1 or 2; pi o and P2 each represents 0, 1, 2, 3 or 4; si and s2 each represents 1 or 2; and t 1 and t 2 each represents 0 or 1, with thr, exclusion of the cases that mi, pi, and tl are simultaneously 0 and that m2, P2, and t 2 are simultaneously 0.

Then, specific examples of the compounds bhown by formula described above are illustrated below but the invention is not limited to these compounds, i 56 A, 3 j 1 HO(CF2)HNOC C-=C -CONH (CH 2 2

OH

~NN, 0 H~OK-'N N f S0 3

K

CkH 2 o S0 3

K

(V 2) HS5C2 oOc f CH4C H=CH Cool-

SO

3

K,

303 K (V 3) KOOC,-*cH-(C=CHCOOK I

I

CH

2

CH.

2 O, 3 3 K03 57 (V 4) HOOC CH- CH= CH COONTA N "N oN uo N..

S03K S 0 3

K

a 0 0 0 0 0~ 0 00 0 0 0 ICON CH=CH I -C OOK N %N oHlNN

CH

2 SS0 3

K

U11 2 6) HsC 2 00C-1 -F-CH- CH-CH 1 COOC 2H

NI

CI

2 8 3

K

58 I IK 0 0 SHZD~~ooos I"H=O-H

OZ

(V 9 INC c C Cl-C =ci-C i 11 1 1 NC uul O-Cu C CN NN N

SOK

SOn r V, NC C C-Cfl CH CH CH O H C 0 ON 11 1 N C Na N No-C c N S 03Na 11) NO C -ct-CH CH =CH -OCH =CH C C Os

I'-

1100 NO S

OOOH

60 12) NC C C=GCH C11 C11 CHI Ci C C CN 11 1 11 1 N C =O HO0- C N N 1-11 X 0 3 S (V 13 NC C C>CH CH CII CH -CII C C CN N 0 HO-C N S0 aN a SO 3.Na (V 14 N C-C CtICH OH -CHI CH rCII iO H 3 C

N

SO H SOoNa 61. NC C C=CHi C11 CH CH C11 C C CN N 0 =0 HO- C N KO0 3 as s 0 3K R 0Oas s 0 3K 16 t 0 NC 0 C-CH CU CU CHU CH C -C ON N "C H0- C N N a03 S N. 0C0H HO0 11000 So a 17 HO0 NN' 0H0-c N OH 2N a N1,303S SO 3 N a 62 ft- -A (v 18) NC C -C=CU ClU Ci CH CH C -C CN N C 0 110 -C N K 0a S 0 K (V 19) 'C C-CH CU CH CH CU C -C CN N C r-0 HO -C N KS SON K (V C C -C-CH CU CU CII CU C -C CN N C U HO -C NHCIzSO:Na NHCHtSOaNa 63 (v -21) NC C -C=C11 Cil CiI C H C11 C -C ON N C =O 110 -C N off H 0 22) CFP C Cc CCH Cil CII CH CHI -C C CIP N C 0 HO- C N (V-23 CP -C otsCell olCII~ H Cil CII C C -CP 0 Cr0 HO- c N V K SOCK SO64 (v 24) 0%1- C -C=CH N N C= 0 COONa C11 C H C H CH -C -C -CF HO -C N CO ON a (v 8 8 8 8 8 C3- C C=CH -CH =CH -CH =CH C=0 HOu -C C CF -c N (CHz) 2

SO

3 Na (v 26) 0 0 CF C C=CH CH CH OF. OH

'N

s 0 2 N H (CHz)zSO3Na O C- C F O NH2 65 (v 27) C C C=CH CHI CHI CHI CHI C C CF 3 N C;=U HO- C

N

cook

KOOC

COON(

(v 28) o 0 3 S 0 00 00 0 00o0 no 0 00 00 0 o 0

CF

3 C -C=CH CHI CHI CHI= CHI C -C

CF

3 11 1 1 1 N C=O0 HO -C

N

O H

COOH

HO0

HOOC

1(03

S

s 03

K

(V 29 CF C C C CH CII C H CIH CI H C C F ii I SO0 3 N a So Na NaO0 3

S

N a 0aS 66 (v

CF

3 -C -C=CH-CH =CH -CH= N N 'C=O0

COOK

CH C C C-

HOCN

COOK

(v -31)

I

4*4444 I I 4 54 I' 4 I 44

I

4 4~ 44 o i.

44 4 4 44 4 44 4 44 '4 4 (4 40 (4(4 (4 o 0 4~4 U 4, '4 0 -P C -C=CH CH =CH CH 11 1 N C0=0 CH -C C-CU 3 HO-C N (CIHZ) ZOH (CHz) z0H 32) HCFzCFz U C N C =-CH CH CH OH =OH C C CPzCFzH 0 HO -C IN S0 3

K

S 3

K

67 33) H (CZ) 4 -C -C=CH Cif=CH -CH =CH -C C (CFz) 4

H

11 1 11 11 N C =O0fl O-CL N SO Na S0 3 N a 444444 4 0 4 44 44 4 4 4*# 4 4 4 4 4 14 4 4 4 4 4 44 ~flQO o 0 0 00 00 0 0 0 0 o (v -34) H C F z-C -C =CH CH C H -CH C H -C -C -C FzH N C 0 HO- C N N

N

SO

3 1y S0 3

K

(v -35) c H NC C -C=CH CH=C; Ch Ch N C=O0 HO s 03 C -C CN

II

C N

I)

0 68 (v 36) I II II I HOCHzCHzNC CHI CHI CHI CHI CH NII~O NN 0 HO0 L;H z LCH z SO Na SO 3 ,Na 0 ft

I

ftft ft ftft ft ft ft 37) HOCHzCHzNC CH- CH N0 SO :IN a

OH

=CH CNCHzCHzOH HO N L;H z SO0 a 69

A

The amount of the compound shown by formula (V) is preferably from 0.0001 g to 1 g, more preferably from 0.0005 g to 0.1 g per square meter of the color photographic material containing the compound.

The dye shown by formula is usually used as an irradiation inhibiting dye. The dye is usually used for silver halide emulsion layer(s), and is particularly preferably used for a green-sensitive emulsion layer or a red-sensitive emulsion layer.

The color developer for use in this invention contains an aromatic amine color developing agent.

Preferred examples thereof are p-phenylenediamine derivatives and specific examples thereof are illustrated below although the invention is not limited to them.

D-l: N,N-Diethyl-p-phenylenediamine o D-2: o D-3: D-4: 4-[N-Ethyl-N-(B-hydroxyethyl)amino]aniline 2-Methyl-4-[N-ethyl-N-(B-hydroxyethyl)aminoaniline D-6: 4-Amino-3-methyl-N-ethyl-N-[B-(methanesulfonamido)ethyl]aniline D-7: sulfonamide D-8: N,N-Dimethyl-p-phenylenediamine D-9: 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline 4-Amino-3-methyl-N-ethyl-N-8ethoxyethylaniline D-ll: 4-Amino-3-methyl-N-ethyl-N-8butoxyethylaniline.

In the aforesaid p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-([-(methanesulfonamido)ethyl]aniline (Compound D-6) is particularly preferred.

Also, these p-phenylenediamine derivatives may be in the form of salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, etc.

0 SThe addition amount of the aromatic primary amine color developing agent is preferably from about o 0.1 g to about 20 g, more preferably from about 0.5 g to about 10 g per liter of the color developer.

The color developer for use in this invention o' can, if necessary, contain an optional development o accelerator. However, from the viewpoints of the inhibition of the occurrence of environmental pollution, 0 0 0 0the easiness of the preparation of solution, the inhibition of the occurrence of magenta, cyan, and 0 o. yellow fogs, and the inhibition of the deviation of D0 0 Sgradation, it is preferred that the color developer contains substantially no benzyl alcohol. The term "contains substantially no benzyl alcohol" means that contains benzyl alcohol in an amount of not higher than 71 -1 ~~i tlt i a I 2 ml per liter of the color developer. It is preferred that the color developer contains no benzyl alcohol.

Also, the color developer may contain, if necessary, other preservative such as sulfites sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metasulfite, potassium metasulfite) and carbonyl-sulfurous acid addition products. The addition amount of the preservative is from 0 g/liter to 20 g/liter, more preferably from 0 g/liter to 5 g/liter. If the preservativity of the color developer is kept, the amount of the preservative is as small as possible from the viewpoints of fog and gradation in the case of, in particular, using the cyan couplers described hereinafter for the color photographic materials being developed.

Other preservatives are hydroxyacetones described in U.S. Patent 3,615,503 and British Patent 1,306,176, a-aminocarbonyl compounds described in JP-A- 52-143020 and JP-A-53-89425, various kinds of metals described in JP-A-57-44148 and JP-A-57-53749, various kinds of saccharides described in JP-A-52-102727, a,a'dicarbonyl compounds described in JP-A-59-160141, salicylic acids described in JP-A-59-180588, and gluconic acid derivatives described in JP-A-56-75647.

4 00 0 04a 00 0nI 6 4 72 These preservatives may be used singly or as a mixture thereof. In particular, the aromatic polyhydroxy compounds are preferred.

The pH of the color developer for use in this invention is preferably from 9 to 12, more preferably from 9 to 11.0. The color developer may further contain other compounds known as components for color developer.

For keeping the aforesaid pH of the color developer, it is preferred to use various kinds of buffers such as carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycine salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, Saminobutyrates, 2-amino-2-methyl-l,3-propanediol salts, valine salts, proline salts, trihydroxyaminomethane salts, lysine salts, etc. In particular, carbonates, oo phosphates, cetraborates, and hydroxybenzoates have such advantages that they are excellent in solubility and also in buffer function in a high pH range of 9.0 or higher, they give no bad influences (fog formation, etc.) on photographic performance when they are added to the color developer, and they are available at low cost, and hence the use of such buffers is preferred.

Specific examples of these buffers are sodium carbonate, potassium carbonate, sodium hydrogen- 73 carbonate, potassium hydrogencarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium 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-2hydroxybenzoate (potassium 5-sulfosalicylate). However, the invention is not limited to these compounds.

The addition amount of the buffer to a color 4 44 p0 4 developer is preferably at least 0.1 mol/lieer, more preferably from 0.1 mol/liter to 0.4 mol/liter.

Dot.

0.4 Moreover, for the color developer for use in 4 44 this invention can be used various chelating agents as a 0 precipitation inhibitor for calcium and magnesium or for improving the stability of the color developer.

As the chelating agent, organic acid compounds are preferred and examples thereof are aminopolycarboxylic acids described in JP-B-48-30496 and JP-B-44- 30232, organic phosphonic acids described in JP-A-56- 973347, JP-B-56-39359, and West German Patent 2,227,639, phosphonocarboxylic acids described in JP-A-52-102726, JP-A-53-42730e JP-A-54-121127, JP-A-55-126241, and JP-A- 55-659506, and the compounds described in JP-A-58- 195845, JP-A-58-203440, and JP-B-53-40900.

74 Specific but non-limitative examples of these chelating agents are nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine o-hydroxyphenylacetic acid, 2-phosphonobutane-l,2,4-tricarboxylic acid, l-hydroxyethylidene- 1,1-diphosphonic acid, and N,N'-bis(2-hydroxybenzyl)- 0o o ethyienediamine-N,N'-diacetic acid.

These chelating agents may be used singly or as a mixture thereof.

The addition amount of the chelating agent may be one sufficient for blocking the metal ions in the ,o color developer and, for example, from about 0.1 g to about 10 g per liter of the color developer.

The color developer may, if necessary, contain an optional development accelerator. However, the color developer for use in this invention contains substantially no benzyl alcohol from the viewpoints of the inhibition of the occurrence of environmental polution and the formation of fog, and the easiness of the preparation of the solution as described above.

75 The compounds of aforesaid formula and the compounds of aforesaid formula (II) or (III) give the remarkable effects in the stability ot the color developer containing substantially no benzyl alcohol.

As other development accelerators, there are thio ether series compounds described in JP-B-37-16088r JP-B-37-5987, JP-B-38-7826, JP-B-44-12380, and 9019, and U.S. Patent 3,913,247, p-phenylenediamine series compounds described in JP-A-52-49829 and 15554, quaternary ammonium salts described in 137726, JP-A-56-156826, JP-A-52-43429, and JP-B-44- 30074, amine series compounds described in JTP-B-41-11431 and U.S. Patents 2,494,903, 3,128,182, 4,230,796, 3;253,919, 2',482t546, 2,596,926, and 3,582,346, polyalkylene oxides described in JP-B-37-16088, JP-B-42- 2520, J-B-41-11431t J-B-42-23883, and U.S. Patents 3,128,183 and 3,532,501, and also I-phenyl-3pyrazolidones and imidazoles.

In this invention, the color developer can, if necessary, contain an optional antifoggant. As the antifoggant, there are alkali metal halides such as sodium chloride, potassium bromide, and potassium iodide and organic antifoggants. Excamples of the organic antifoggant are nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, -76- A isoindazole, 5-methylbenzotriazole, azole, 5-chlorobenzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolidine, and adenine.

It is preferred that the color developer for use in this invention contains a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'diamino-2,2'-disulfostilbene series compounds are preferred. The addition amount thereof is from 0 to g/liter, preferably from 0.1 g/liter to 4 g/liter.

Also, if necessary, the color developer for use in this invention may further contain various kinds of surface active agents such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, aromatic carboxylic acids, etc.

The processing temperature for the color developer in this invention is preferably from 20 0 C to 50 0 C, more 0 0% preferably from 30 0 C to 40 0 C and the processing time is preferably 0 0 from 20 seconds to 5 minutes, preferably from 30 seconds to 2 minutes. The replenishing amount is preferably less but is usually from 20 ml to 600 ml, preferably oOO. from 50 ml to 300 ml, and more preferably from 100 ml to 0 200 ml per square meter of the color photographic material being processed.

I 77 7 p.

I-

o 0 0 0 pr pr P 0 00 0 (0 001 Then, a bleaching solution, a bleach-fix (blix) solution, and a fix solution for use in this invention are explained.

As the fixing agent for the bleach solution or blix solution, any conventional bleaching agents can be used. In particular, organic complex salts of iron(III) iron(III) complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc., aminophosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids); organic acids such as citric acid, tartaric acid, malic acid, etc.; persulfates; hydrogen peroxide, etc.

In these bleaching agents, the organic complex salts of iron(III) are particularly preferred from the viewpoints of quick processing and the prevention of the occurrence of environmental polution.

Useful aminopolycarboxylic acids, aminopolyphosphonic acids, and organic phosphonic acids for forming the organic complex salts of iron(III) are, for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methylimino- 78 Then, a bleaching solution, a bleach-fix (blix) solution, and a fix solution for use in this invention are explained.

As the fixing agent for the bleach solution or blix solution, any conventional bleaching agents can be used. In particular, organic complex salts of iron(III) iron(III) complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc., aminophosphonic 0 o acids, phosphonocarboxylic acids, and organic phosphonic acids); organic acids such as citric acid, tartaric acid, malic acid, etc.; persulfates; hydrogen peroxide, etc.

In these bleaching agents, the organic complex salts of iron(III) are particularly preferred from the o viewpoints of quick processing and the prevention of the occurrence of environmental polution.

Useful aminopolycarboxylic acids, aminopolyphosphonic acids, and organic phosphonic acids for forming the organic complex salts of iron(III) are, for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cy::lohexanediaminetetraacetic acid, methylimino- 78

I

diacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid.

These compounds may be in the form of sodium salts, potassium salts, lithium salts, or ammonium salts. In these compounds, the iron(III) complex satls of ethylelendiaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred from the viewpoint of "oo showing high bleaching power.

0 The ferric ion complex salt may be used in the form of the complex salt or may be formed in an aqueous 4 solution by using a ferric salt such as ferric sulfate, 9 0 ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc., and a chelating agent o such as amonopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc. In this case, the chelating agent may be used in an excessive amount to the formation of the ferric complex salt. In the ferric complex salts, the ferric complex salt of amino- 0 polycarboxylic acid is preferred and the addition amount thereof is from 0.01 mol/liter to 1.0 mol/liter, more preferably from 0.05 mol/liter to 0.50 mol/liter.

79 t K For bleach solution, a blix solution and/or a pre-bath therefor can be used various compounds as a bleach accelerator. Examples thereof are the compounds having a mercapto group or a disulfide bond described in U.S. Patent 3,893,858, German Patent 1,290,812, JP-A-53- 95630, and Research Disclosure, No. 17129 (July, 1978), thiourea compounds described in JP-B-45-8506, JP-A-52- 20832, JP-A-53-32735, and U.S. Patent 3,706,561, and halides such as iodine ions, bromine ions, etc. They 0 are excellent in bleaching power.

00 a 00 The bleach solution or blix solution for use in this' invention may further contain a rehalogenating 44 agent such as bromides potassium bromide, sodium bromide, ammonium bromide), chlorides potassium chloride, sodium chloride, ammonium chloride), and oiodides ammonium iodide). Furthermore, if necessary, the bleach solution or the blix solution may contain a corrosion inhibitor such as inorganic or organic acids having a pH buffer faculty or the alkali metal salts and ammnonium salts of thr~s acids 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) ammonium nitrate, guanidine, etc.

I

As a fixing agent for the blix solution or the fix solution being used in this invention, there are conventional fixing agents such as thiosulfates sodium thiosulfate, ammonium thiosulfate), thiocyanates sodium thiocyanate, ammonium thiocyanate), thioether compounds ethylenebisthioglycolic acid, 3,6-dithia-l,8-octanediol), and thioureas known as water-soluble silver halide solvents. They can be used singly or as a mixture thereof. Also, specific blix 0 solutions composed of a combination of a fixing agent «4 o and a large amount of halides such as potassium iodide is described in JP-A-55-155354 can be used. 'In this invention, the use of thiosulfates, in particular ammonium thiosulfate is preferred.

0.o The amount of the fixing agent is preferably 000 0 from 0.3 mol to 2 mols, more preferably from 0.5 mol to mol per liter of the blix solution or the fix Ssolution. The pH range of the blix solution or the fix solution is preferably from 3 to 10, more preferably from 5 to 9.

Also, the blix solution can further contain various kinds of fluorescent whitening agents, defoaming agents or surface active agents, polyvinylpyrrolidone, and organic solvents such as methanol, etc.

81

I

The blix solution or the fix solution further contains a sulfite ion releasing compound such as sulfites sodium sulfite, potassium sulfite, ammonium sulfite), hydrogensulfites ammonium hydrogensulfite, sodium hydrogensulfite, potassium hydrogensulfite), and metahydrogensulfites potassium metahydrogensulfite, sodium metahydrogensulfite, ammonium metahydrogensulfite) as a preservative.

So The content of the compound is preferably from on 0.02 mol/liter to 0.50 mol/liter, more preferably from 0.04 mol/liter to 0.40 mol/liter.

As the preservative, sulfites are generally added but, ascorbic acid, a carbonyl-hydrogensulfurous acid addition product, or a carbonyl compound may be o o used.

Furthermore, the blix solution or the fix solution may, if necessary, contain a buffer, a fluorescent whitening agent, a chelating agent, a defoaming agent, a fungicidal agent, etc.

In this invention, after desilvering processing such as blixing or fixing, the silver halide color photographic material is generally washed and/or stabilized.

82 The amount of wash water in the wash step is selected in a wide range according to various conditions such as the characteristics (by the materials being used, such as couplers, etc,,) and uses of the color photographic materials, the temperature of wash water, the replenishing system such as countercurrent system and concurrent system. The relation of the number of wash tanks and the amount of wash water can be determined by the method described in Journal of the Society of Motion Picture and Television Engineers, Vol.

o 64, 248-253 (1955). The stage number of the tanks in a multistage countercurrent system is preferably from 2 to 6, particularly from 2 to 4.

By a multistage countercurrent system, the amount of wash water can be greatly reduced, for 0 0 0 1O example, to 0.5 liter to 1 liter per square meter of the color photographic material being processed but in this case, the increase of the residence time of water in the tanks is accompanied with a problem of growing bacteria and attaching floats formed onto the color photographic materials.

For solving the aforesaid problem, a method of reducing calcium and magnesium described in JP-A-62- 288838 can be very effectively used. Also, isothiazolone compounds and thiabendazoles described in 83 1 _i CJL 1

I

JP-A-57-8542, chlorine series sterilizers such as chlorinated sodium isocyanurates described in JP-A-61- 120145, benzotriazoles described in JP-A-61-267761, copper ions, and the sterilizers described in Hiroshi Horiguchi, Bokin Bobaizai no Kagaku (Chemistry of Antibacterial and Antifungal Agents), Biseibutsu no Mekkin, Sakkin, Bobai Gijutsu (Antibacterial and Antifungal Technique of Microorganisms), edited by Eisei Gijutsu Kai, and Bokin Bobaizai Jiten (Handbook of Antibacterial and Antifungal Agents) can be used.

rFurthermore, for wash water can be used a so surface active agent as a wetting agen't and a chelating o agent such as ethylenediaminetetraacetic acid (EDTA) as Ca a water softener.

The pH of wash water in the processing process of this invention is from 4 to 9, preferably from 5 to 8. The temperature and time for the wash step can be selected properly according to the properties and the use of the color photographic materials being processed but are generally from 20 seconds and 10 minutes at from 0 C to 45 0 C and preferably from 30 seconds to 5 minutes at from 25°C to 40 0

C.

After the aforesaid wash step or without employing the wash step, the color photographic materials can be processed by a stabilization solution.

84 A. i i a .1 The stabilization solution contains a compound having a function of stabilizing images formed, such as an aldehyde compound formalin), a buffer for controlling the pH of layers, and an ammonium compound.

Also, for preventing the growth of bacteria in the solution and imparting an antifungal property to the photographic material after processing, the various kinds of sterilizers or antifungal agents described above can be used.

o Furthermore, the stabilization solution may o ii> contain a surface active agent, a fluorescent whitening agent, a hardening agent, etc. When the stabilization is directly performed without employing wash step, the processes described in JP-A-57-8543, JP-A-58-14834, JPgon A-59-184343, JP-A-60-220345, JP-A-60-238832, 239784, JP-A-60-239749, JP-A-61-4054, and JP-A-61-118749 can be used.

o Furthermore, in a preferred embodiment of this invention, a chelating agent such as 1-hydroxyethylidene-l,l-diphosphonic acid, ethylenediaminotetramethylenephosphonic acid, etc., or a magnesium or bismuth compound can be used kor the stabilization solution.

The solution used for the wash step and/or the stabilization step can be used for the pre-step. As on 85 example thereof, there is a process wherein the overflow of wash water, the amount of which is reduced by a multistage countercurrent system, is supplied to a blix bath which is the pre-bath of the wash step and a concentrated solution is applied to the blix bath to reduce the amount of the waste solution.

The process of this invention can be applied to any processing processes using a color developer. For example, the invention can be applied to processing of color photographic papers, color reversal photographic papers, direct positive color photographic materials, color positive photographic films, color negative photographic films, color reversal photographic films, etc., but the invention is particularly preferably applied to processing of color photographic papers and color reversal photographic papers.

The silver halide emulsion for the color photographic materials being processied by the process of this invention is composed of silver iodobromide, silver bromide, silver chlorobromide, silver chloride, etc.

For example, in the case of performing quick processing or low-replenishing process of color photographic papers, etc., a silver chlorobromide emulsion or silver chloride emulsion containing at least 60 mol% silver chloride is preferred and further the case that the 86 content of silver chloride is from 80 mol% to 100 mol% is particularly preferred. Also, when a high speed is required and also the formation of fog at the production, storage, and/or processing the color photographic materials is kept at particularly low, a silver chlorobromide emulsion or silver bromide emulsion containing at least 50 mol% silver bromide (the emulsion may contain not higher than 3 mol% silver iodide) is preferred and the aforesaid emulsion containing at least 70 mol% silver bromide is more preferred.

0 SFor color photographic materials for camera use, a silver iodobromide emulsion or a silver chloroiodobromide emulsion is preferred and in this case, the content of silver iodide is preferably from 3 to mol%.

The silver halide grains for use in this invention may have different phases between the inside o and the surface layer thereof, may have a multiphase structure having a junction structure, or may be composed of a uniform phase throughout the whole grain.

Also, the silver halide grains may be composed of a mixture thereof.

The mean grain size (shown by the diameter of the grains when the grain is spherical or similar to spherical, and shown by the mean value based on the 87 a% -A projected area using, in the case of cubic grains, the long side length as the grain size, or further shown by the mean value calculated as circle in the case of tabular grains) of the silver halide grains for use in this invention is preferably in the range of from 0.1 pm to 2 pm, particularly preferably from 0.15 pm to 1.5 pm.

The grain size distribution of the silver halide grains may be narrow or broad but the use of a so-called monodispersed silver halide emulsion, wherein the value (coefficient of variation) obtained by dividing the Sstandard deviation in the grain size distribution curve 1o 00 of the silver halide emulsion by the mean grain size of the silver halide grains in the emulsion is within (preferably within is preferred. Also, for satisfying the desired gradation for the color photographic materials, two or more kinds of monodispersed silver halide emulsions (preferably having the above-described coefficient of variation) each having aifferent grain sizes can be used as a mixture thereof for one emulsion layer or as separate emulsion layers each having substantially the same color sensitivity.

Furthermore, two or more kinds of polydispersed silver halide emulsions or a combination of the monodispersed silver halide emulsion and a polydispersed silver halide 88 tI L^ emulsion can be used as a mixture thereof for one emulsion layer or as separate emulsion layers.

The silver halide grains for use in this invention may have a regular crystal form such as cubic, octahedral, dodecahedral, tetradecahedral, etc., a mixture thereof, an irregular crystal form such as spherical, etc., or a composite form of these crystal forms. Also, the silver halide grains may be tabular grains and in this case, a tabular grain silver halide emulsion wherein tabular grains having an aspect ratio (length/thickness) of from 5 to 8 or 8 or more account for at least 50% of the total projected area of the silver halide grains can be used in this invention. A mixture of these silver halide emulsions each containing silver halide grains having different crystal forms may be also used. The silver halide emulsion may be of a surface latent image type of forming latent images mainly on the surface thereof or of an internal latent image type of forming latent images mainly in the inside of the grains.

The silver halide emulsions for use in this invention can be prepared by the methods described in Research Disclosure Vol. 176, No. 17643, I, II, and III (December, 1978).

89 L 1 I The emulsion for use in this invention is usually chemically ripened and spectrally sensitized after physical ripening. The additives being used in such steps are described in Research Disclosure, Vol.

176, No. 17643 (December, 1978), and ibid., Vol. 187, No. 18716 (November, 1979) and the corresponding portions thereof are shown in the following table together with other photographic additives for use in this invention.

ii vi ci 90 L i i I 1 1 Additive 1. Chemical sensitizer 2. Sensitivity increasing agent 3. Spectral sensitizer RD 17643 Page 23 RD 18716 Page 648, right column Pages 23-24 i) 00 00l O C i) C 0 00u 4. Supersensitizer Whitening agent 6. Antifoggant and stabilizer 7. Coupler 8. Organic solvent 9. Light absorbent, filter dye, ultraviolet absorbent Stain inhibitor 11. Dye image stabilizer 12. Hardening agent 13. Binder 14. Plasticizer, lubricant Coating aid and surface active agent 16. Static inhibitor Page 24 Pages 24-25 Page Page Pages 25-26 Page 25, right column Page Page 26 Page 26 Page 27 Pages 26-27 Page 27 Page 648, right column to page 649, right column Page 649, right column Page 649, right column Page 649, right column to page 650, left column Page 650, left to right columns Page 651, left column It Page 650, right column it 91 -n .1

J

In this invention, various color couplers can be used for color photographic materials being processed.

The term "color coupler" means a compound capable of forming a dye by causing coupling reaction with the oxidation product of an aromatic primary amine color developing agent. Typical examples of the useful coupler are naphtholic or phenolic couplers, pyrazolone or pyrazoloazole series compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples e o oof the cyan magenta and yellow couplers for use in this invention are described in the patents cited in Research Disclosure, No. 17643, VII-D (December, 1978) and ibid., No. 18717 (November, 1979).

It is preferred that the color couplers contained in the color photographic materials are rendered non-diffusible by a ballast group or by being polymerized. Furthermore, the use of 2-equivalent color 0 couplers, the coupling active site of which is substituted by a releasing group, is more effective for reducing the amount of silver thAn the case of using 4equivalent color couplers having a hydrogen atom at the coupling- active e thereof. Couplers providing colored dyes having a proper diffusibility, non-coloring couplers, DIR couplers releasing a development inhibitor with the coupling reaction, and couplers releasing a S92 92 i1. 3 development accelerator with the coupling reaction can be also used.

Typical examples of the yellow couplers for use in this invention are oil-protect type acylacetamide series couplers. Specific examples thereof are described in U.S. Patents 2,407,210, 2,875,057, and 3,265,506.

In this invention, 2-equivalent yellow couplers are preferably used and typical examples thereof are 0 0 0 oxygen atom-releasing type yellow couplers described in U.S. Patents 3,408,194, 3,447,928, 3,933,501, and 4,022,620 and nitrogen atom-releasing type yellow Scouplers described in JP-B-55-10739, U.S. Patents 4,401,752 and 4,326,024, British Patent 1,425,020, West German Patent Application (OLS) Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812, and Research Disclosure, No. 18053 (April, 1979). In these couplers, a-pivaloylacetanilide series couplers are excellent in fastness, in parLicular, light fastness of the colored dyes formed, while a-benzoylacetanilide series yellow couplers give high coloring density.

As the magenta couplers for use in this invention, there are oil-protect type inadazolone series and cyanoacetyl series couplers, preferably S93 93 r. lil I- t~L 1 series couplers and pyrazoloazole series couplers such as pyrazolotriazole series couplers.

The 5-pyrazolone series couplers having an arylamino group or an acylamino group at the 3-position thereof are preferred from the viewpoint of the hue of the colored dyes and typical examples 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 releasing groups for the 2-equivalent T° 5-pyrazolone series magenta couplers include nitrogen atom-releasing groups described in U.S. Patent 4,310,619 o and arylthio groups described in U.S. Patent 4,351,897.

Also, 5-pyrazolone series magenta couplers having a ballast group described in European Patent 73,636 give soo, high coloring density.

o Pyrazoloazole series magenta couplers include pyrazolobenzimidazoles described in U.S. Patent 1 0 0 Cu a 3,369,879, preferably pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Patent 3,725,067, pyrazolotetrazoles oo described in Research Disclosure, No. 24220, (June, C i 1984), and pyrazolopyrazoles described in Research Disclosure, No. 24230 (June, 1984). From the viewpoint of less yellow side absorption of colored dyes and high light fastness of colored dyes, imidazo[l,2-b]pyrazoles described in European Patent 119,741 are preferred and -94pyrazolo[l,5-b][l,2,4]triazoles described in European Patent 119,860 are particularly preferred.

Cyan couplers for use in this invention include oil-protect type naphtholic and phenolic couplers, and typical examples are naphtholic couplers described in U.S. Patent 2,474,293, preferably oxygen atom-releasing type 2-equivalent naphtholic couplers described in U.S.

Patents 4,052,212, 4,146,396, 4,228,233, and 4,296,200.

Also, specific examples of the phenolic cyan couplers 2 are described in U.S. Patents 2,369,929, 2,801,171, 0 2,772,162, and 2,895,826. Cyan couplers having high o fastness to moisture and heat are preferably used in this invention, and typical examples thereof are the phenolic cyan couplers having an alkyl group of two or more carbon atoms at the meta-position of the phenol nucleus described in U.S. Patent 3,772,002, diacylamino-substituted phenolic cyan couplers described 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 JP-A-59-166956, and phenolic cyan couplers having a phenylureido group at the 2position and an acylamino group at the thereof described in U.S. Patents 3,446,622, 4,333,999, 4,451,559, and 4,427,767.

95 In particular, in the processing process of this invention, good photographic properties with less formation of fog can be obtained by using at least one kind of cyan couplers shown by following formula which is also a specific effect.

OH

R

33

NHCOR

31

R

3 2 Z 1 1 4 wherein R31 represents an alkyl group, a cycloalkyl group, an aryl group, an amino group, or a heterocyclic group; R32 represents an acylamino group or an alkyl group having 2 or more carbon atoms; R33 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group; R32 and R33 may combine with each other to form a ring; and Zll represents a hydrogen atom, a halogen atom or a group capable of being released at the S° reaction with the oxidation product of an aromatic 0 primary amine color developing agent.

The alkyl group shown by R31 in formula is preferably an alkyl group having from 1 to 32 carbon atoms methyl, butyl, tridecyl, cyclohexyl, 96 allyl), examples of the aryl group shown by R 3 1 are phenyl and naphthyl, and examples of the heterocyclic group are 2-pyridyl and 2-furyl.

When R31 in formula is an amino group, a phenyl-substituted amino group which may be further substituted is preferred.

The groups shown by R3 1 may be substituted by an alkyl group, an aryl group, an alkyloxy or aryloxy group methoxy, dodecyloxy, methoxyethoxy, phenyloxy, 2,4-di-tert-aiaylphenoxy, 3-tert-butyl-4-hydroxyphenyloxy, naphthyloxy) a carboxy group, an alkylcarbonyl or arylcarbonyl group acetyl, tetradecanoyl, benzoyl), an alkyloxycarbonyl or aryloxycarbon group methoxycarbo'yl, phu4noxycarbonyl), an acyloxy group acetoxy, benzoyloxy), a sulfamoyl group N-ethylsulfamoyl, N-octadecylsulfamoyl), a carbamoyl group N-ethylcarbamoyl, N-methyldodecylcarbamoyl),- a sulfonamido group methanesulfonamido, benzenesulfonamido), an acylamino group acetylamino, benzamido, ethoxycarbonylamino, phenylaminocarbonylamino), an inmido group succinimido, hydantoinyl), a sulfonyl group methanesulfonyl), a hydroxyl group, a cyano group, a nitro group, or a halogen atom.

-97 In formula Z11 represents a hydrogen atom or a coupling releasing group such as, for example, a halogen atom fluorine, chlorine, bromine), an alkoxy group dodecyloxy, methoxycarbamoylmethoxy, carboxypropyloxy, methylsulfonylmethoxy), an aryloxy group 4-chlorophenoxy, 4-methoxyphenjxy), an acyloxy group acetoxy, tetradecanoyloxy, benzoyloxy), a sulfonyloxy group methanesulfonyloxy, toluenesulfonyloxy), an amido group dichloroacetylamino, methanesulfonylamino, toluenesulfonylamino), an alkoxycarbonyloxy group ethoxycarbonyloxyr benzyloxycarbonyloxy), an aryloxycarbonyloxy group phenoxycarbonyloxy), an aliphatic or aromatic thio group phenylthio, tetrazolylthio), an imido group succinimido, hydantoinyl), an N- 0 heterocyclic group 1-pyrazolyl, l-benztriazole), or an aromatic azo group phenylazo). These releasing groups may contain a photographically useful group.

on c. ~The compounds shown by formula may form a dimer or a more polymer at R31 or R3 2 Then, specific examples of the cyan couilers shown by formula are illustrated below but the invention is not limited to them.

-98

-I-

pF-~t 7 66 0~ U

U

0 0 (0 00 0 (0 00 0' 00 00 0 0 0 ~00 ~(00 0 o)01000,1N1 6HvD

HO

.L H gD( l)

/OHPODHN

9H z1 HO1 (C-3 c Y

C

2

H

5 NHCOC I 3

H

2 7 (n) (c C2H (t)cSH 1 1

C,

cC C co J 11 o0

C

4 H9 cSi-rI c-

OH

Cz NTFCO(CH 2 3 0/ c 2

H

5 C

OCH

2

CH-

2

CH

2

COOH

C C -6) NElCOC 3 F 7 (tOcS1 1 1 *(t)cSH 1 1

I

loo C -7

NHCQ-//

C

1 I 2

H

2 -oi-ic1

(C

C

12

H.

2 OCHCONH/i c z

I

NIICO (t)C 4 H9 U U

U

U

c~ o

U

~U U U

U

U U 0

U

-9

U

U

CAH

1 (t)c 5

H

1 1

OCHCONH

cze

NHCO~(V

U

00 o MC3Ct F F 101

(C

-ii) OH

NHCO

I fwSO 2

C

4

H

9

C

5 HM OCHCOINH) (C-12) OH~ K <o 17

I

o/0 OCHCONH

N

(t)c 6

E

1

NHC~

aNSO,)CH 2

)CH

2 0CH 3 o P 0 P o o o 0 0 0 0 o ~j 0 p 0 0 0 4 (C-1 3) Hco Q

ENISO

2

(CH

2 4 0-

)CH

(C-14)

PC,

C,

0 0 CH5 CHS O NHCOr IV Hs0 2

C

1 6

HSS

H

CL.

102 I A A i

I

0 ki OH

NN

N

0

RI

N\HCQCEO /C5 I (t)c 5

H

1 1 (016)

H

N

(C-17)

CH

3

QH

N c4e

C

8 HI 7 RN S02' C 2

HS

0 #0 0 0 0# NICO -F\ 2

H

0NHCOCHO /P -t H (t)CH 5 1 1 103

A

(0-18) NiSO 2 C 16 H 33 (n) (C-19) i)f~0, Op ft 0 0 2-fso \>C125n

O

C 4

H

9 NCOH<jN (tc SH 1 OCHO4Ni N: (t)c SHIi

I

0 0 (C-21 (t)CAr 7 104 l (C-22) NHCONRB So 2 c 3 1 7 (t~cH 11

C

2

H

(t CHCO 1 1 (C-23) 0OH c1i WtC 5 1

OCECONK

(tc 5 H 11 #04000 0 0 04 I 4 4 00 4044 '4 o (C-24) 0 0OCHS 105 (KIEi 0 (t)C 8

H

1 7

(Q~C

8 H 17 0a~, 00(50 (C-26) NHCONH

S

5

HI

1 03 The cyan couplers shown by formula can be synthesized based on the descriptions in JP-A-59-166956 and JP-B-49-lJ.572.

In this invention, the graininess of the color images formed can be improved by using a coupler giving colored dye havIng a proper diffusibility together with the aforesaid couplers(s). About such couplers giving 106 diffusible dyes, specific examples of the magenta couplers are described in U.S. Patent 4,366,237 and British Patent 2,125,570 and specific examples of the yellow, magenta and cyan couplers are described in European Patent 96,570 and West German Patent Application (OLS) No. 3,234,533.

The dye-forming couplers and the specific couplers described above may form a dimer or polymer.

Typical examples of the polymerized dye-forming couplers o are described in U.S. Patents 3,451,820 and 4,080,211.

Also, specific examples of the polymerized magenta couplers are described in British Patent 2,102,173 and U.S. Patent 4,367,282.

The couplers for use in this invention can be used for one light-sensitive emulsion layer as a mixture of two or more for meeting the properties required for the color photographic material or the same kind of o 0' coupler may be incorporated in two or more photographic layers.

So The coupler for use in this invention can be o introduced into silver halide emulsions by an oil dropin-water dispersion method. Examples of a high-boiling organic solvent being used for the oil drop-in-water dispersion method are described in U.S. Patent 2,322,027. Also, the coupler can be introduced into the 107 silver halide emulsions by a latex dispersion method and specific examples of the step and the effect of the latex dispersion method and the latex for the impregnation are described in U.S. Patent 4,199,363 and West German Patent Application (OLS) Nos. 2,341,274 and 2,541,230.

A standard amount of the color coupler is in the range of from 0.001 mol to 1 mol per mol of the lightsensitive silver halide in the silver halide emulsion, with from 0.01 mol to 0.5 mol of a yellow coupler, from o 0.003 mol to 0.3 mol of a magenta coupler, and from 0.002 mol to 0.3 mol of a cyan coupler, per mol of the light-sensitive silver halide being preferred.

The color photographic materials being processed by the process of this invention is prepared by coating eo i S the aforesaid emulsions, etc., on a flexible support 0 00 such as plastic films (films of cellulose nitrate, o cellulose acetate, polyethylene terephthalate, etc.), papers, etc., or a solid support such as glass plates, etc.

SDetailed of such supports and. the coating methods are described in Research Disclosure, Vol. 176, No. 17643, XV (page 27) and XVII (page 28) (December, 1978).

108 L The process of this invention is preferably applied to color photographic materials using reflective supports. The "reflective support" is a support having high reflectivity for clearly viewing color images forming in silver halide emulsion layer(s) and includes a support coated with a hydrophobic resin having dispersed therein a light reflective material such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc., and a support composed of a hydrophobic 2 resin containing the light reflective material described above.

The inven:tion is now illustrated in detail with reference to the following examples but the invention is not limited thereto.

EXAMPLE 1 A color Developer having the following composition was prepared.

o" s Color Developer Compound (Compounds of formulae (II) Shown in and (III) Table 1 below Compound (Compound of formula Shown in Table 1 Sodium Sulfite 0.2 g Potassium Carbonate 30 g Disodium Ethylenediaminetetraacetate 1 g 109 4-Amino-3-methyl-N-ethyl-N-[0-(methane- 5.0 g sulfonamido)ethyl]aniline Sulfate Whitening Agent (4,4'-diaminostilbene 3.0 g series, UVITEX-CK®, made by Chiba- Geigy AG) Water to make 1 liter pH 10.05 Thus, Samples No. 1 to No. 17 of color developer were prepared. Each of the samples was placed in a test tube so that the opening ratio (opening area/sample area) became 0.02 cm-1 and stirred for 4 weeks while controlling to 35°C. After 4 weeks, the volume of water reduced by evaporation was supplemented by distilled on r water and the residual rate of the aromatic primary °o ,amine color developing agent in the developer was measured by liquid chromatography. The results obtained are shown in Table 1.

o 0 0 01,,

U&

04 0 4o 0 t 0 4 U' 110 Table 1.

Sample Compound Compound Residual No. (0.03 mol/e) 4 mol/e) Rate* 3

M%

Note Comparison 11 1-7 1-12 Triethanol- N,N-diethylamine (II-1) hydroxylamine L.4t. 4 4 4 O 44 4 0 4 4 Lb 4 44 4 Lb Lb 4140 I I 0 4 44 4 o 4 4 Lb 44 4'2L44 4 4 0~ 4 4 Polyethyleneimine* 4 111-7 6 11-2.

7 11-3 8 111-1 9 111-7 .0 11-i .1 11-3 L2 111-1 L3 111-7 A4 11-1.

I r- It 1-7 i 1-1.2 1-22 1-25 1-48 1-49 11 Invention it it The compounds are shown by the compounds shown above.

The compounds are shown by the compounds shown above.

number of number of III 11A 1 Residual rate(%) of color developing agent

(A)

x *4:tCH2CH2NHtn n=500 to 2,000 As is clear from the results shown in Table 1, it can be seen that the residual rate is insufficient in the case of using the compound of formula alone (Sample Nos. 1 and 2) and the residual rate is not sufficient even in the case of using the polyethyleneimine such as triethanolamine or the compound such as Compound III-7 together with N,N-diethylhydroxylamine (Sample Nos. 3, 4, and However, as is clear from the results of Sample Nos. 6 to 17 of this invention, it can be seen that by the use of the compound shown by formula (II) or (III) together with oa the compound of formula the residual rate of the a°o color developing agent is greatly improved, which shows 0 the preservativity of the color developer being improved.

EXAMPLE 2 By following the same pLocedure as Example 1 except that Compound 1-28, 1-44, 1-58 or 1-60 was used in place of Compound 1-7 in Sample Nos. 6 and 7, almost same preferred results were obtained.

112 iy~J a -1 EXAMPLE 3 By following the same procedure as Example 1 except that Compound II-4, II-5, 11-10 or 11-15 and Compound III-2, III-5, III-8 or III-11 were used in place of Compound II-3 and Compound III-1 in Sample Nos.

7 and 8, almost the same results were obtained.

EXAMPLE 4 A multilayer color photographic paper having the following layers on a paper support having polyethylene coating on both surfaces thereof was prepared.

The coating compositions for the layer were prepared as follows.

Preparation of Coating C6mpositions In 27.2 ml of ethyl acetate and 7.7 ml (8.0 g) of a high-boiling solvent (Solv-1) were dissolved 19.1 g of a yellow coupler (ExY-1) and 4.4 g of a color image stabilizer (Cpd-1) and the solution was dispersed by So emulsification in 185 ml of an aqueous 10% gelatin solution containing 8 ml of a solution of 10% sodium dodecylbenzenesulfonate. The emulsified dispersion was mixed with silver halide emulsions EM 7 and EM 8 and 4 the gelatin concentration was adjusted as shown below to provide the coating composition for Layer 1. The coating compositions for Layers 2 to 7 were prepared by the similar manner as above. For each layer was used 1- 113 i ~i i sodium salt as a gelatin hardening agent. Also, for each layer was used Compound (Cpd-l) as a thickener.

Layer Structure The composition of each layer was shown below.

The numeral shows the coating amount (g/m 2 wherein a silver halide emulsion is shown by the coating amount calculated as silver.

In addition, the polyethylene coating at the emulsion side contained a white pigment (TiO 2 and a bluish dye.

Layer 1 Blue-sensitive Emulsion Layer Monodispersed silver chlorobromide 0.15 emulsion (EM 7) spectrally sensitized by sensitizing dye (ExS-1) Monodispersed silver chlorobromide 0.15 emulsion (EM 8) spectrally sensitized by sensitizing dye (ExS-1) Gelatin 1.86 Yellow coupler (ExY-1) 0.82 Color image stabilizer (Cpd-2) 0.19 Solvent (Solv-1) 0.35 Layer 2 Color Mixing Inhibiting Layer QXlatin 0.99 Color mixing inhibitor (Cpd-3) 0.08 114 i* Layer 3 Green-sensitive Emulsion LzAyer Monodispersed silver chiorobromide 0.12 emulsion (EM 9) spectrally sensitized by sensitizing dyes (ExS-2 and 3) Monodispersed silver chiorobromide 0.24 emulsion (EM 10) spectrally sensitized by sensitizing dyes (ExS-2 and 3) Gelatin 1.24 Magenta coupler (ExM-l) 0.39 Color image stabilizer (Cpd-4) 0.25 Color image stabilizer (Cpd-5) 0.12 Solvent (Solv-2) 0.*25 Layer 4 Ultraviolet Absorption Layer Gelatin 1.60 Ultr.Ayiolet absorbents (Cpd-6/Cpd-7/ 0.70 Cpd-8=3/2/6 by weight ratio) Color mixing inhibitor (Cpcl-9) 0.05 Solvent (Solv-3) 0.42 Layer 5 Red-sensitive Emulsion Layer Monodispersed silver chlorobromide 0.07 emulsion (EM 11) spectrally sensitized by sensitizing dyes (ExS-4 and Monodispersed silver chlorobromide 0.16 emulsion (EM 12) spectrally sensitized by sensitizing dyes (ExS-4 and Gelatin 0.92 Cyan coupler (ExC-l) 1.46 Cyan Coupler (1ExC-2) 1.84 Color image stabilizers (cpd-7/Cpd-8/ 0.17 Cpd-10=3/4/2 by weight ratio) -115- I i Dispersing polymer (Cpd-ll) 0.14 Solvent (Solv-l) 0.*20 Laver 6 Ultraviolet Absorption Layer Gelatin 0.54 Ultraviolet absorbents (Cpd-6/Cpd--8/ 0.21 Cpd-10=1/5/3 by weight ratio) Solvent (Solv-4) 0.08 Layer 7 Protective Layer Gelatin 1.33 Acryl-modified copolymer of po:lyvinyl 0.17 alcohol (modification degree 17%) Liquid paraffin 0.03 Also, in this case, Compounds (Cpd-12 and Cpd- 13) were used as irradiation inhibiting dyes.

Furthe'rmore, for each layer Alkanol XCID (trade name, made by DuPont), sodium alkylbenzenesulfonate, and Magefacxlm F-120 (trade name, made by Dainippon ink and Chemicals, Inc.) were used as emulsion-dispersing agent ~'and coating aid. LFurther, Compounus (Cpcl-14 and were used as stabilizers of the silver halides.

The details of the silver halide emulsions used were as follows.

Emulsion EM 7 EM 8 EM 9 EM 10 EM 11 EM 12 Grain Form Size (Pim) Cubic 1.1 Cubic 0.8 Cubic 0.45 Cubic 0.34 Cubic 0.45 Cubic 0.34 Coefficient Br-Content of variation* (M01%) 1.0 0.10 1.0 0.10 1.5 0.09 1.5 0.09 1.5 0.09 1.6 0.10

C,

0 standard deviation/mean grain size, which shows the distribution of grains.

The compounds used are as follows.

ExY-.

(M1 3 C U 5 3A '0c 2 11 .117 M EXIM- I nC I H 27

COINEHC

N7 0 OiNO C s Ii Cz 4~~H O ExS -1

(CH

2 4 S0 3 (CH 2 soE(CH) C) 4 C, Cl 1

CH=

(CH'

2 4

S

(O

2 4 SOB ElN(C 2 1 5 3 ES-3

C

2

H

CH=O-CHi~ Nc.

(OH

S 0 3 ITh1$~ 119

ZI-

)Ifos t) (000 1 L 0; 005-U)

T

00 0 0 00 00 0 0 00 0 0 0 0 0 to 0 ~0 0 0 0 0 *0 0 *0 0 0 0 00 0 0 0 0*0 0 J4 1o 9 14 ZO CIN= 4

HD

Cpd-2 Cl%CH; 0 11 C COO N-CCHi=CH 2

CHS

CH

3 2 Cpd-3 0 0 C8 H 17 (sec) (sec)CBH 1 7

OH.

Cpd-4 t ~D0 ICF1

C

3

H

7 0 C 3

H

7

OH

3 0CSH 7 .121 Cp d OH GH 3 IH C- C 2 -)-5-COOC 6

HI

13 C H 1 3 00C CH ICH 3

CH

3

OH

OH C Hq(t) 04

N

C 4

H

9 (t) 0 0

OH

c 4 i(t) -122 A C p d 8 OH C 4 H9 (s ec)

C

4

H

9 (t) C pd 9 -C 8

H

17 (t) 0 0 0 0 (t)cBHI 7' Cp d- 0 a OH C 4

H

9 (t)

CH

2

CH

2

COOC

8 Hl 7 0 (1 0 Cpd-11

UONUC

4 H (t) n t 10 0- 1000) 123 C p d- 12

H

5

C

2 00CH-CH=CH-CHCH~ 7 COOC 2

H

S0 3 K S0 3

K

4-I I a

I

o I a a C p d-13 HO 0

SO

3 K S 03 K oIl a S 01 aa lll a a a a) I C pd- 14

OH

3 1-4 N OH I 124 A, N NHCONHCH3

SH

C C cC C C C OC C 0) '0 Solv-1 Dibutyl phthalate Solv-2 Trioctyl phosphate Solv-3 Trinonyl phosphate Solv-4 Tricresyl phosphate Each of the color photographic papers obtained was wedge-exposed and process in the following processing steps, wherein a running processing test (coitinuous processing test) was performed on various color developers until the amount of the replenisher for the color developer became 3 times the volume of the tank.

C

Processing Step Color Development Blix Rinse (1) Rinse (2) Rinse (3) Drying Temperature 35 0

C

35 0

C

30 0

C

JoC 30 0

C

60-70 0

C

Time 45 sec.

45 sec.

20 sec.

20 sec.

20 sec.

30 sec.

Replenisher Amount 160 ml/m2' 100 ml/m 2 200 ml/m2 125 The rinse was performed by a cour.,'.ercurrent system of from Rinse to Rinse The composition of each processing solution used was as follows.

Color Developer Tank Replenisher Additives C and D Shown in Table 2 Fluorescent Whitening Agent 3.0 g 4.0 g (4,4-diaminostilbene series) Ethylenediaminetetraacetic 1.0 g 1.5 g Acid Potassium Carbonate 30.0 g 30.0 g Sodium Chloride 1.4 g 0.1 g 4-Amino-3-methyl-N-ethyl-N-[O- 5.0 g 7.0 g (methanesulfonamido) ethyl) aniline Sulfate Benzyl Alcohol Shown in Table 2 Diethylene GlYcol Shown in Table 2 010 ,2-Dihydroxybenzene-3,4,6- 300 mng 300 mg trisulforiic Acid Water to make 1 liter 1 liter PH 10.10 10.50 Blix Solution (The composition of the tank solution was same as ,hat of the replenisher.) EDTA Fe(III)NH4,2H 2 0 60 g EDTA 2Na*2H204 Ammonium Thiosulfate 120 ml Sodium Sulfite 16 g Glacial Acetic Acid 7 g -126 Water to make 1 liter pH Rinse Solutions and (3) (The composition of the tank solution was same as that of the replenisher.) Ethylenediamine-N,N,N',N'- 0.3 g tetramethylenephosphonic Acid Benzotriazole 1.0 g Water to make 1 liter pH adjusted by KOH to 7.50 The aforesaid processing steps were carried out using the aforesaid processing solutions and the B(blue), G(green), and R(red) densities (stains) at the unexposed portions of each sample at the start of the running processing and at the end of the running processing were measured using a self densitometer, made by Fuji Photo Film Co., Ltd. Furthermore, after allowing to stand each sample at the end of the running processing for "onths at 80 0 C (5 to 10 RH), the B, G, and R densities were measured again.

The changes of the photographic properties obtained ar. shown in Table 2 below.

127 L 1 A 7-.

Table 2 Tank Liauid Re~lenisher Test Re-i~v Diethylene Benzyl Diethylene No. Alcohol Glycol Alcohol Glycol (Ml) Emil (l Additive C Additive D (0.04 mol) (0.03 mol) H,N-Di- Triethanolethyl- amine hydroxyl- (11-1) amine 1-7- 1-7- 1-12- 1-7 I- Thnin Increase* Dmin Increase* (at the end (After 2 months of Running) at 80 0

C)

B G R B G R Note +0.05 +0.04 +0.01 +0.25 +0.18 +0.05 Comparison +0.07 +0.05 +0.05 +0.03 +0.01 0 0 +0.01 +0.04 +0.03 +0.02 +0.01 0 0 0 0 +0.01 0 0 0 0 0 0 0 +0.27 +0.21 +0.22 +0.17 +0.15 +0.15 +0.15 +0.14 +0.20 +0.12 +0.10 +0.09 +0.08 +0.07 +0.08 +0.07 +0.07 +0.06 +0.05 +0.05 +0.04 +0.03 +0.04 +0.03

H

Invention

HI

111-1 1-12 7if Ta~ble 2 (cont'd) Additive C Additive D (0.04 mol) (003 mol) Tank Licuid Test Beazyl Diethylene No- Alcohol Glycol (ml) (ML) Reolenisher Benzyl Diethylene Alcohol Glycol (sal) Dmin Increase* Dmin Increase* (at the end (After 2 months of Running) at B G R B G R Note Invention 1-12 1-22 1-25 1-48 111-7 0 0 0 +0.13 +0.07 +0.03 11-1 +0.01 0 0 +0.16 +0.08 +0.05 11-1 +0.01 0 0 +0.15 +0.08 +0.04 11-i +0.02 0 0 +0.17 +0.08 +0.05 1 13- Increased Drnin to the Pmi~n at thie start of running processing.

From the results shown in Table 2 above, it can be seen that in Test Nos. 1 to 4, the formation of stains is greatly increased as the result of the running processing, whereas in Test Nos. 5 to 13, the increase of stains is very few. Also, it can be seen that in the change of the photographic properties with the passage of time after processing is very less in Test Nos. 5 to 13 as compared with Test Nos. 1 to 4.

EXAMPLE A multilayer color photographic paper having the following layers on a paper support having polyethylene coating on both surfaces was prepared.

Preparation of the coating compositions for layers In 27.2 ml of ethyl acetate and 7.7 ml (8.0 g) of a high-boiling solvent (Solv-l) were dissolved 19.1 g of a yellow coupler (ExY-1) and 4.4 g of a color image stabilizer (Cpd-1) and the solution was dispersed by emulsification in 185 ml of an aqueous 10% gelatin solution containing a solution of 10% sodium dodecylbenzenesulfonate. The emulsified emulsion was mixed with silver halide emulsions EM 7 and EM 8 and the gelatin concentration was adjusted as shown below to provide the coating composition for Layer 1. The 130

A

coating compositions for Layer 2 to Layer 7 were also prepared by the similar manner to above.

Layer Structure The composition of each layer was shown below, wherein the numeral shows the coating amount (g/m 2 in which the amount of the silver halide emulsion is shown by the coating amount of silver calculated.

In this case, the polyethylene coating at the emulsion side contains a white pigment (TiO2) and a bluish dye.

Layer- Blue-sensitive Emulsion Layer Monodispersed silver chlorobromide 0.15 emulsion (EM 7) spectrally sensitized by sensitizing dye (shown in Table 3) Monodispersed silver chlorobromide 0.15 emulsion (EM 8) spectrally sensitized by sensitizing dye (shown in Table 3) Gelatin 1.86 Yellow coupler (Ex-l) 0.82 Color image stabilizer (Cpd-2) 0.19 Solvent (Solv-l) 0.35 Layer _2 Color Mixing Inhibiting Layer Gelatin 0.99 Color mixing inhibitor (Cpd-3) 0.08 La 3 .g3 Green-sensitive Emulsion Layer Monodispersed silver chlorobromide 0.12 emulsion (EM 9) spectrally sensitized by sensitizing dye(s) (shown in Table 3) 131 Monodispersed silver chlorobromide 0.24 emulsion (EM 10) spectrally sensitized by sensitizing dye(s) (shown in Table 3) Gelatin 1.24 Magenta coupler (ExM-1) 0.39 Color image stabilizer (Cpd-4) 0.25 Color image stabilizer (Cpd-5) 0.12 Solvent (Solv-2) 0.25 Layer 4 Ultraviolet Absorption Layer Gelatin 1.60 Ultraviolet absorbents (Cpd-6/Cpd-7/ 0.70 OCpd-8=3/2/6 by weight ratio) oO° Color mixing inhibitor (Cpd-9) 0.05 o*.

0 Solvent (Sclv-3) 0.42 0 Layer 5 Red-sensitive Emulsion Layer Monodispersed silver chlorobromide 0.07 emulsion (EM 11) spectrally sensitized by sensitizing dyes (shown in Table 3 and Monodispersed silver chlorobromide 0.16 emulsion (EM 12) spectrally sensitized by sensitizing dyes (shown in Table 3 on" and Gelatin 0.92 o Cyan coupler (ExC-1) 1.46 00 Cyan Coupler (ExC-2) 1.84 Color image stabilizers (Cpd-7/Cpd-8/ 0.17 Cpd-10=3/4/2 by weight ratio) Dispersing polymer (Cpd-ll) 0.14 Solvent (Solv-1) 0.20 132 Layer 6 Ultraviolet Absorption Layer Gelatin 0.54 Ultraviolet absorbents (Cpd-6/Cpd-8/ 0.21 Cpd-10=l/5/3 by weight ratio) Solvent (Solv-4) 0.08 Layer 7 Protective Layer Gelatin 1.33 Acryl-modified copolymer of polyvinyl 0.17 alcohol (modification degree 17%) Liquid paraffin 0.03 For each layer were used Alkanol XC® -(trade name, made by DuPont), sodium alkylbenzenesulfonate, a o'0ao succinic acid ester, and Magefacx® F-120 (trade name, 0 *0 0 o0 made by Dainippon Ink and Chemicals, Inc.) as 0o 0 o emulsification dispersing agent and coating aids. Also, "o "o for each layer were used Compounds Cpd-14 and 15 as stabilizers of the silver halides.

o 0 The details of the silver halide emulsions used o 0 are as follows.

0 0 133 Emulsion EM 7 EM 8 EM 9 EM 10 EM 11 EM 12 Grain Form Size FP rn) Cubic 1.1 Cubic 0.8 Cubic 0.45 Cubic 0.34 Cubic 0.45 Cubic 0.34 Coefficient Br-Content of variation* (mol%) 1.0 0.10 1.0 0.10 1.5 0.09 1.5 0.09 1.5 0.09 1.6 0.10 Same as above.

The compounds used above are as follows.

000000 0 ~0 00 0 0 00 0 o o 0 00 0 0 00 0 V 00 0 0 00 V 00 ExY-l

C

5

H

1 1 t 0OC 2

H

0000 0 0000 134 A I I ML---A Ix ExM-1 nCl 3

H

27 CONH C.

NH,_

C

2

E

NHCOCHO (t)C 5

H

11

C

5

H

11

CE

3 C 0 C 0 0 0 C 135 ExC-2

CH

5 NHCO (tC 5 H 1 OCHCONH I "71 Cl Cl Cpd-1 tCH 2 -CHtn I (n=500 to 1,000) I)0 3

K

Cpd-2

HO/

(t)C0H 9

CH

3 136 I I m A Cpd-3

OH

-C

8 Hl 7 (sec) (sec)CE 1 7

'N

OH

Cpd-4 444'' CE CE 3

C

3

H

7 0 'NO

C

3

H

7

CE

3

CE

3

CH

0 0C p OH 4H CHTt273OC1 4!3 CHd C~O CE 3 ~tC

C

6 1 3 00C-Cj) 3 C OH

CE

3 -137-

A

Cpd-6 OH C 4

H

9 (t)

N~

ClN I N

C

4

H

9 (t) Cpd-7

OH

NI N NN I Cpd-8 OH C 4

H

9 (sec)

C

4 H,(sec) 13 138 Cpd-9

OH

C0 17

N

OH

I IN

'N-

OH C 4

H

9 (t)

CH

2

CH

2 cooc 8 Hl 7 o4,q4~ Cpd-1.

0 0 0 00 0 00 4 0 00 (CH -CH-~ LCONkiC 4

H

9 t) (n=100-1000) Cpd-14 00 0 0 00 0 CH N

OH

139 N=N; NHCONHCH 3

SH

Solv-1 Dibuty. phthalate Solv-2 Triocty. phosphate Solv-3 Trinonyl phosphate SoJlv-4 Tricresy. phosphate 0 KY~ro ~NH CH YOz~ N N SO 3

H

Cl

Y

0 Each of Samples 2-F, 2-G, 2-H, 2-1, 2-J, and 2-K were prepared by changing the sensitizing dyes and the irradiation inhibiting dyes as shown in Table 3 below.

140 /1 2 a is is is is isis is C, is is 0 isis isisis isisQ Table 3 Blue- Sensitive Layer Sensitizing Dye Green- Redsensitive Layer sensitive Layer Sample Irrradiation Inhibiting Dye (amounb mg/n 2 2-F NaO 3 SHCNH 0 H L N SO 3 Na NaO 3 S N OH 0 NHCH 2 so 3 Na (8) j8) IIIa-41 II Ib-3 5 IIIb-3 6 IIIa-42 NaQ 3

S

2-G

SO

3 Na II Ia-4 1 IIIb-36 IIla- 42 NaO 3 s' OH 0 SO 3 Na 2-H V-2 v-4 V-36 V-37 (4) (4) (4) S-A S-B S-C 2-I S-A S-B S-C -L 0 0 0 r, c o a 0 Table 3 Sample Irrradiation Ini,-ibitin4 Dye (amount mg/n 2 2-J V-2 V-4 V-3 6 V-37 (4) (4) (4) Sensitive Layer IIIa-41 IIIa-41 Sensitizing Dye Green- Redsensitive Layer sensitive Layer IIIa-42 IIIa-42 2-K 0 N

S

0I~ 0 0 44 00 44 4 4 4

S-B

C z 115 I 0 C 2if 0c If d 00 -4 44 S-c 0c 2 11 Gi1 cII CII cif =011 C 2115 -143 Iff a 41

(I

2 0 0 0 0 Co 0000 SOu3HN (C 2 HS) 3 III a -'42) 01 If C If 00 L; 2 115

I

144 (IIM b 0

-CH

U(CH Z) 4 .S v a ZO 0 a aa 0 (0 0 0 ~.a a 4. 0 4.4.4.4 4. .4.

4. 4.

4.4 kLCIt 2 4- S0aHN (CzHs) 3 (II[ b 36) 4.4.4.4.

4. 4 4.

4. Qa 0 4. 4.

1 04.

4 0 0o 4.4.

4 4.

0 c zH CH=C-CUh

N

(C;h z) zSO 3 L;It 2

IOHN

145 At Each of the color photographic papers thus obtained was subjected to a wedge-exposure and running processing (continuous processing) as in Example 4.

In this case, however, the color developer only having the following composition was used.

Color Developer Tank Replenisher Additives A and B Shown in Table 4 Fluorescent Whitening Agent 3.0 g 4.0 g S(4,4-diaminostilbene series) °Coo Ethylenediaminetetraacetic Acid 1.0 g 1.5 g Potassium Carbonate 30.0 g 30.0 g Sodium Chloride 1.4 g 0.1 g 4-Amino-3-methyl-N-ethyl-N-[B-- 5.0 g 7.0 g (methanesulfonamido)ethyl]aniline Sulfate 1,2-Dihydroxybenzene-3,4,6- 300 mg 300 mg trisulfonic acid Water to make 1 liter 1 liter pH 10.10 10.50 After processing as in Example 4, the change (ADmin) of the minimum densities at the start of the running test and at the end thereof was measured. The results are shown in Table 4.

146 S. I_ r7 a a so a a,' *a a c *0 4 a a 0 a 4' 0 a 0 0 Table 4 Test No.

2 3 4 6 7 8 9 11 Additive A (0.04 mol) N, N-Dimethylhydroxylamine of It to Additive B (0.03 mol) 2-F ADmin

B

+0.05

G

+0.04

R

+0.05 1-7 If 2-G 2- (H) 2- (I) 2-F 2-G 2-F 2-G 2- (H) 2- (1) 2- (J) +0.06 +0.05 +0-.07 +0.04 +0.04 +0.04 +0 .06 +0.06 +0.06 +0.07 +0.04 +0.06 Note Comparison Invention 1I +0.06 +0.04 +0.05 11-1 of +0.01 +0.02 0 0 +0.01 +0.01 +0.01 0 0 0 +0 .02 +0 .01 0 0 0 '0 0 .0 0 a a a 0 a a o 0 a Q Table 4 (cont'd) Additive A Test No. (0.04 mol) 12 1-7 13 1-7 14 If o 16

I

17 1-12 18 If Additive B (0.03 mol)_ ADmin SamPi e*l 2- (K) 2-F 2-G 2- (H) 2- (1) 2-G 2- (H) B G 0 0 +0.01 +0.01 +0.01 0 0 0 0 0 +0.02 0 0 0 R Note 0 Invention +0.01 I +0.01 +0.01 The samples containing the compound of formula are parenthesized.

As is clear from the results shown in Table 4, it can be seen that the cases of using the compound of formula together with the compound of formula (II) or (III) (including the cases of using the samples containing or not containing the compound of formula (Test Nos. 7 to 18) according to this invention show less change of stain as compared to the cases of using N,N-dimethylhydroxylamine (Test Nos. 1 to 4) and the cases of using the compound of formula alone (Test Nos. 5 and In particular, it can be also seen that the aforesaid effect is more remarkable in the "o I cases of using the compound of formula together with the compound of formula (II) or (III) and processing the samples containing the compound of formula (Test o Nos. 9 to 12, 15, 16, and 18) as compared to even the cases of using the compound of formula together with the compound of formula (II) or (III) and processing the samples containing no compound of formula (Test Nos.

7, 8, 13, 14, and 17).

EXAMPLE 6 A multilayer color photographic paper having the layer structure shown below on a paper support having polyethylene coating on both surfaces thereof was prepared. The coating compositions for the layers were prepared by mixing each silver halide emulsion, various 149 ft- A chemicals, and each emulsified dispersion of coupler(s) as follows.

Preparation of coupler emulsion: In 27.2 ml of ethyl acetate and 7.7 ml of a solvent (Solv-1) were dissolved 19.1 g of a yellow coupler (ExY) and 4.4 g of a color image stabilizer (Cpd-l) and the solution was dispersed by emulsification in 185 ml of an aqueous 10% gelatin solution of 8 ml of a solution of 10% sodium dodecylbenzenesulfonate.

Also, by the similar manner to above, a magenta 0 0a emulsion, a cyan emulsion, and each emulsion for each o o interlayer were prepared.

The compounds used for the emulsions are shown below.

(ExY) Yellow coupler

CH

3 Cl

CH

3 -C-CO-CH-CONH C 5

H

1 t 0 3 NHCOCHO-

C

5

H

11 t 0 N CA2 150 (ExM-1) Magenta coupler Cl

NH

C

1 3H 2 7 CONH N/ 0 I'll o o ~O f a (ExC-l) Cyan coupler ttr.

0 4 0 04

(L)CSH

11 44 4 0 (t)CSH 11 151 ExC-2) Cyani coupler

NHCO/

C1 4 4 4 44 44 4 4 44 4 44 44 4 4444 4 44 4 4 44 *4 4 4 4I 44,, 44 44 4 4 44 44 4 o 0 o 4444* 4 9 (Cpd-1) Color image stabilizer

C

4

H

9 (t) HO

C

4

H

9 (t)

CH

2 C COO 2 04 4 4 4 4 4 4 44 (Cpd-2) Color mixing inhibitor

OH

R

OH

R=C

8

H

1 7 (SeC) 152 -139- (Cpd-3)

C

3

H

7 0

C-

3

CH

3

C

3

H

7 0 'NO

C

3

H

7 0C 3

H

7

CH

3

CH-

3 4 (Cpd-4) OH '~3

-TCH

2

T

3 cOOC 6

HI

3

CH

3 I CH

C~-

13 00tC 2 t 3

C

CH

3 ACpd-_51 Color mixing inhibitor Same as Cpd-2; R=COH1 7 (t) -153- _(Cpd-6) Color image stabilizer A 5:8:9 (by weight) mixture oE 6a, 6b and 6c.

C

4

H

9 (t) 0 0

C)

o 0 0 0 0 ~o C 4

H

9 It) 0 N

C

4 H9(sec)

C

4 H t) 0 0 (Cpd-7) Polymer CONHCk' 4 k 9 t) Average molecular weight: 80,000 154

I

(UV-1 Ultraviolet absorbent A 2:9:8 (by weight) rnixtur, of Cpd-6a, 6b and 6c.

0 C, 0 Q 0 000 o Oo 04 (Solv-1) Solvent

COO,

4

H

9

~COOC

4

H

9 (Solv-2) Solvent O=PtO-CBH 17 (iSO) 3 -(Solv-3) Solvent 0 O=ptj-C 9

H

19 )3 155 (Solv-4) Solvent

CH

3 O=Pt03 _C )3 Also, for irradiation inhibition, the following dyes are used for the silver halide emulsion layers.

For Red-Sensitive Layer: Dye-R o o a HO OH o HOCH 2

CH

2 N C CHCH=Cn C NCH 2

CH

2

OH

N O HO, N I

I

CH

2 CH 2

-SO

3 Na SOaNa wherein n=2 For Green Sensitive Layer: Same as Dye-R (wherein, however, n is 1) Also, for the red-sensitive emulsion layer was used the following compound in an amount of 2.6xl0- 3 mol per mol of the silver halide.

1S<3

"D

Al1 i

I

NYO <yNNH-

CH

NN<^N S0 3 1H 0^ 2 The silver halide emulsions for use in the o a '0 example were prepared as follows.

Blue-Sensitive Emulsion: A monodispersed cubic silver chloride emulsion (containing K21rC16 and having a mean grain size of 1.1 pm and a coefficient of variation of 0.10 was prepared by a conventional method.

To 10 kg of the emulsion was added 26 ml of a 0.6% solution of a spectral blue-sensitizing dye a fine grain silver bromide emulsion having a mean grain size of 0.05 pm was added to the host silver chloride emulsion in an amount of 0.5 mol% to the host emulsion followed by performing ripening, sodium thiosulfate was added to perform the optimum chemical sensitization, and then a stabilizer (shown in Table A below) was added thereto in an amount of 10-4 mol per mol of silver to provide the blue-sensitive emulsion.

157 0, 0 o CC o o 0, u

CC

Green-Sensitive Emulsion: After preparing silver chloride grains containing K2IC16 and 1,3-dimethylimidazolin-2-thione by a conventional manner, 4x10- 4 mol/mol-Ag of a sensitizing dye and KBr were added to the emulsion followed by ripening, and after adding thereto sodium thiosulfate to perform the optimum chemical sensitization, 5x10- 4 mol/mol-Ag of a stabilizer (shown in Table A below) was added thereto to provide a mono-dispersed cubic silver chloride emulsion having a mean grain size of 0.48 pm and a coefficient of variation of 0.10.

Red-Sensitive Emulsion: By following the same manner as the case of preparing the green-sensitive emulsion while using 1.5x10- 4 mol/mol-Ag of a sensitizing dye was used in place of the sensitizing dye a red-sensitive emulsion was prepared.

The sensitizing dyes used are shown below.

158 L i _i I, i i *I 1 Sensitizing Dye S

S

ci N

N

"C

2 3 (CEr 2 2 1S1o E

Q

0 0 o ~o c' 0 o 0 00 0 ~O 0 0 Sensitizl,,g Dye (CI Sensitizin~g dye 000 0I0 0 0 0

>=CH-

Ii C;2H 1 2

E

159 Layer structure The composition of the layers are shown below, wherein the numeral is the coating amount '(g/m 2 in which the amount of a silver halide emulsion is shown by the amount of silver calculated.

In addition, the polyethylene coating on the emulsion side contained a white pigment (TiO 2 and a bluish dye (ultramarine blue).

Layer 1 Blue-sensitive Emulsion Layer o Silver Halide Emulsion 0.25 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-l) 0.19 Solvent (Solv-l) 0.35 Layer 2 Color Mixing Inhibiting Layer Gelatin 0.99 Color mixing inhibitor (Cpd-2) 0.08 Layer 3 Green-sensitive Emulsion Layer Silver Halide Emulsion 0.31 Gelatin 1.24 Magenta coupler (FxM-l) 0.31 Color image stabilizer (Cpd-3) 0.25 Col.. image stabilizer (Cpd-4) 0.12 Solvent (Solv-2) 0.42 160 M A Layer 4 Ultraviolet Absorption Layer Gelatin 1.58 Ultraviolet absorbents (UV-1) 0.62 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-3) 0.24 Layer 5 Red-sensitive Emulsion Layer Silver Halide Emulsion 0.21 Gelatin 1.34 .o Cyan coupler (a blend of ExC-1 0.34 Oa and C-2 at 1:1) Color image stabilizer (Cpd-6) 0.17 Polymer (Cpd-7) 0.40 Solvent (Solv-4) 0.23 Layer 6 Ultraviolet Absorption Layer Gelatin 0.53 Ultraviolet absorbents (UV-1) 0.21 Solvent (Solv-3) 0.08 Layer 7 Protective Layct SGelatin 1.33 o o Aryl-modified copolymer of polyvinyl 0.17 alcohol (modification degree 17%) Liquid paraffin 0.03 For each layer was used triazine sodium salt as a hardening agent.

Thus, Sample A was prepared. Furthermore, by following the same procedure as above while changing the 161 Ak1 I I Sijli stabilizer as shown in Table A below, Samples B, C, D, E, F, and G were also prepared.

Table A Sample Stabilizer Amount (mol/mol-Ag) a I 0 -0 00 a np D 6~ t o a-i a-2 a-3 IV-27 IV-46 (a-2) 10-4

'I

II

'I

(a-1) (a-3)

OH

H

3

N

H

OaN

H

H

3 CN

H

H

Each of the samples thus prepared was imagewise exposed and then subjected to continuous processing (running test) by the following processing steps and the processing compositions until the amount of the replenisher for the color developer supplied became 162 i i twice the volume of the tank for the color developer.

In this case, however, the composition of the color developer was changed as shown in Table 5 below for each running test.

Also, the processed amount per day was, in average, 2.5 m 2 of the color photographic paper.

The processing step employed was as follows.

0 Replenisher Tank o Processing Step Temp. Time Amount Volume Color Development 38°C 45 sec. 100 ml 8 liters Blix 350C 45 sec. 161 ml 8 liters Rinse 350C 20 sec. 4 liters Rinse 350C 20 sec. 4 liters Rinse 35 0 C 20 sec. 4 liters Rinse 350C 30 sec. 200 ml 4 liters Drying 80 0 C 60 sec.

The replenisher amount was per m 2 of the color photographic paper.

Also, the rinse was performed by a 4 tank countercurrent system of from Rinse to Rinse The compositions of the processing solutions were as follows.

Color Developer Tank Replenisher Water 800 ml 800 ml 163 A .i i, i a Methyltriethylenediamine 5.0 g 5.0 g (l,4-diazabicyclo[2, 2,2joctane) Compound (shown in Table 5) 50 mmols 58 minds Ethylenediamine-N,N,N',N'- 3.0 g 4.0 g tetramethylenephosphonic Acid Sodium Chloride 1.9 g 0 g Potassium Carbonate 30.0 g 30.0 g 4-Amino-3-methyl-N-ethyl(5- 5.4 g 7.2 g inethanesulfonarnidoethyl) -3iethyl-4-aminoaniline Sulfate *Water to make 1 liter I liter pH20)10.10 10.50 Blix Solution (The composition of the tank solution was same as that of the replenisher.) EDTA Fe(III)NH 4 '2H 2 O 60 g EDTA*2Na*2H20 4 g Sodium Thiosulfate 120 ml 4,Sodium Sulfite 16 g Glacial Acetic Acid 7 g Water to make 1 liter 4PH (25 0 C) Rinse Solution (The composmtion of the tank solution was same as that of the replenisher.) Ion-exchanged water (no imre than 3 ppm of each of Ca and Mg) Water to make I liter PH -164- Then, each of the samples prepared was subjected to gradation exposure of photographic paper for sensitocnety using a sensitometer (Type FWE, made by Fuji Photo Film Co.., Ltd., color temperature of light source: 3200 0 In this case, the exposure was performed so that the exposure amount became 250 CMS at an exposure time of 1/10 second.

At the end of the running test, the aforesaid sensitometry was performed and the minimum densities 0:2: (T)min) of yellow, magenta, and cyan and the maximum 0 II density (Dmax) of yellow were measured using a Macbeth densitometer. The results obtained are shown in Table 4 165 424 0

I.

*0 4, 4, 0 44 4, ~4, 4,0 4, 0 0 44 4, 44 0 0 4, 4, 4, 4, 4, 04,4, t Table Test No.

1 2 3 4 6 7 8 9 11 12 13 14 Sample

A

B

F

G

A

B

F

G

B

G

Compound (IV) Compound (I) Diethylhydroxylamine IV-45 IV-46& c-Hydroxyketone it IV-4 5 IV-46 IV-46 Yellow 0.41 0.20 0.19 0.17 0.40 0.20 0.13 0.13 0.18 0.16 0.41 0.19 0.21 0.19 Dmin Magenta 0.45 0.21 0.19 0.18 0.43 0.20 0.14 0.13 0.19 0.17 0.40 0.19 0.19 0.18 Cyan 0.45 0.20 0.17 0.18 0.43 0.21 0.13 0.13 0.19 0.17 0.41 0.19 0.18 0.20 Dmax Yellow 2.40 2.38 2.37 2.37 2.56 2.51 2.52 2.51 1.48 1.45 2.55 2,50 2.51 2.51 Comparison Hydroxylamine Is 1-7 it kh-- 0 a 'CC a 0 4 4. 00a q Table 5 (cont'd) Test No.

16 17 18 19 21 22 23 24 26 27 Sample

E

F

G

is is It it Be Compound (IV) IV-27 IV-45 IV-46 If is IV-45 to IjV-27 it Compound 1-7 Is It 1-12 1-22 1-25 1-28 1-44 1-48 1-49 1-58 1-60 1-8 Yellow 0.10 0.09 0.09 0.10 0.08 0.09 0.10 0.09 0.08 0.09 0.10 0.10 0.11 Dmin Magenta 0.09 0.10 0.11 0.10 0.09 0.11 0.12 0.09 0.08 0.09 0.11 0.10 0.09 Cyan 0.10 0.11 0.12 0.11 0.09 0.11 0.09 0.10 0.10 0.09 0.10 0.11 0.09 Dmax Yellow 2.50 2.50 2.52 2.51 2.52 2.53 2.51 2.51 2.53 2.49 2.52 2.53 2.59 Invention '3

'I

It

'I

Is It of '3 (IHydroxyketone is the compound shown 0 CHCH0 by the formula As is clear from Table 5, it can be seen that in the cases of using the compound of formula together with the compound of formula (IV) (Test Nos. 15 to 27), Dmin is greatly improved as compared to the cases of using the compound of formula or (IV) solely (Test Nos. 3, 4, 11, 12, 13, and 14). Also, it can be seen that when a hydroxylamine which is conventionally used for color developer is used in place of the compound of formula a sufficient effect is not obtained in the system of using together the compound of formula (IV) and, in particular, in the case of using hydroxylamine, Dmax is greatly reduced (Test Nos. 9 to ooEXAMPLE 7 When the same procedure as Example 6 was followed while using each of Compounds IV-10, IV-ll, IV- 14, IV-22, IV-28, and IV-47 in place of Compound in Sample F in Test No. 16, similar preferred results were obtained.

004 0 °a 0 EXAMPLE 8 A multilayer color photographic paper having the following layer structure on a paper support having polyethylene coating on both surfaces thereof was prepared. The coating compositions for the layer were prepared as follows.

168

J

Preparation of Coating Compositions In 27.2 ml of ethyl acetate and 7.7 ml of a high-boiling solvent (Solv-1) were dissolved 10.2 g of a yellow coupler (ExY-1), 9.1 g Oc a yellow coupler (ExYand 4.4 g of a color image stabilizer (Cpd-1) and the solution was dispersed by emulsification in 185 ml of an aqueous 10% gelatin solution containing 8 ml of a solution of 10% sodium dodecylbenzenesulfonate. The ,o°o emulsification dispersion was mixed with Emulsions EM 1 o°o and EM 2 and the gelatin concentration was adjusted as shown below to provide the coating composition for Layer 1.

The coating compositions for Layer 2 to Layer 7 were also prepared by the similar manner to above.

For each layer was used 4triazine sodium salt as a gelatin hardening agent.

Also, Compound (Cpd-2) was used as a thickener.

Layer Structure The composition of each layer was shown below.

The numeral shows the coating amount (g/m 2 wherein the amount of silver halide emulsion is shown by the amount of silver calculated.

In addition, the polyethylene coating at the emulsion side contained a white pigment (TIO2) and a bluish dye.

169- fL. A Layer 1 Blue-sensitive Emulsion Layer Monodispersed silver chlorobromide 0.13 emulsion (EM 1) spectrally sensitized by sensitizing dye (ExS-1) Monodispersed silver chlorobromide 0.13 emulsion (EM 2) spectrally sensitized by sensitizing dye (ExS-1) Gelatin 1.86 Yellow coupler (ExY-1) 0.44 Yellow coupler (ExY-2) 0.39 Color image stabilizer (Cpd-1) 0.19 0 0 Solvent (Solv-1) 0.35 Layer 2 Color Mixing Inhibition Layer Gelatin 0.99 Color mixing inhibitor (Cpd-3) 0.08 Layer 3 Green-sensitive Emulsion Layer Monodispersed silver shlorobromide 0.05 emulsion (EM 3) spectrally sensitized by sensitizing dyes (ExS-2 and 3) Monodispersed silver chlorobromide 0.11 emulsion (EM 4) spectrally sensitized by sensitizing dyes (ZxS-2 and 3) o Gelatin 1.80 Magenta coupler (ExM-1) 0.39 Color image stabilizer (Cpd-4) 0.20 Color image stabilizer (Cpd-5) 0.02 Color image stabilizer (Cpd-6) 0.03 Solvent (Solv-2) 0.12 Solvent (Solv-3) 0.25 170 A-L _i i Layer 4 Ultraviolet Absorption Layer Gelatin 1.60 Ultraviolet absorbents (Cpd-7/Cpd-8/Cpd-9 0.70 =3/2/6 by weight ratio) Color image inhibitor (Cpd-10) 0.05 Solvent (Solv-4) 0.27 Layer 5 Red-sensitive Emulsion Layer Monodispersed silver chlorobromide 0.07 emulsion (EM 5) spectrally sensitized 4 by sensitizing dyes (ExS-4 and 9 .o Monodispersed silver chlorobromide 0.16 emulsion (EM 6) spectrally sensitized by sensitizing dyes (ExS-4 and Gelatin 0.92 Cyan coupler (ExC-1) 0.32 o Color image stabilizers (Cpd-8/ 0.17 .4o Cpd-9/Cpd-12=3/4/2 by weight) Dispersing polymer (Cpd-11) 0.28 Solvent (Solv-2) 0.20 Lavr 6 Ultraviolet Absorption Layer So Gelatin 0.54 Ultraviolet absorbents (Cpd-7/Cpd-9/ 0.21 Cpd-12=1/5/3 by weight ratio) Solvent (Solv-2) 0.08 Layer Protective Layer Gelatin 1.33 Acryl-modified copolymer of polyvinyl 0.17 alcohol (modification degree 17%) Liquid paraffin 0.03 i I -I i a~ 1 For each layer were used Compounds Cpd-14'and as irradiation preventing dyes. Also, for each layer were used Alkanol Ba (trade name, made by DuPont), sodium alkylbenzenesulfonate, a succinic acid ester, and Magefacx F-120 (trade name, made by Dainippon Ink and Chemicals, Inc.) as emulsification dispersing agent and coating aids. Further, for each layer was used each of e' the compounds shown in Table B as a stabilizer of the jo( silver halides.

o 00 Grain Coefficient 0oo° Emulsion Form Size Br-Content of variation* o. o (pm) (mol%) a ato a a EM 1 Cubic 1.0 80 0.06 EM 2 Cubic 0.75 80 0.07 a 0. EM 3 Cubic 0.5 83 0.09 oo EM 4 Cubic 0.4 83 0.10 EM 5 Cubic 0.5 73 0.09 EM 6 Cubic 0.4 73 0.10 0 *A Same as above The compounds Used are as follows.

Ex Y- 1

CU

(CI) CCOCHCOMH

,CCO[CH/

I CH NH[OCHO

CH

11 t

C

2

H-

I H c H, 2 CHO -ce N H a H 2 cH 2

OC

2

HS

NNHSO 2 0 alH 17

CHO/

N H SO 2 a H 1 17~3 I VIII.- A

T

E x C I c CHOCH2 E x S I [ICOCi sH3i(n) c H

(CH

2 4 SOo- (G l 2 4 S03HN(C 2 Hs)3 E x S 2 C 2 H h=L-CHl 0 0 0 0 00 3SO2- 174 E x S 3 c H

(CH

2 4 SU 3 (C H 2 )4Q SOAN (C 2

H

E x S 4 0 400 0 oo 0 oo 0 0 6040

CII

C A Si C 2

H

I-,Ex S- 2 175 C p d- I (t) (t) rA'- 4 9 coo lI=CH 2 u 4 n9 COp d 2 COp d- -C aH 7(sec) 0000 4 (sec) CoH 7 176 44-. J" C p d 0 C/ C4 3 H7 C As (t n CU d

CONH(CH

2 )3 0 CHIt CS 11 1 M(t -177 9LT -I u* i, 6

J~

(D29) 6 fp, G~p 0) 6

H~:

p d D

N

a 8-PdD 0 o 4 0 0 Ot' 4 0 0 0 010 ),-Pd C p d Ica H I 0 C p d -11 I. a

LONHL

4

H

9 (t) n 100 -1000) C p d -12 c 9 AHs (M H 2 CH2 C00C O II SolV'-1 Dibuty. Phthalate Solv-2 Tricresy. Phosphate SoJlv-3 Triocty. Phosphate Solv-4 Trinonyl Phosphate 179 "L -A C p d -13 HO0 I II

HOCH

2 cU 2

NC

-CH =CH -CH =CH 11 3 IN a ANa 0 a C p d -14

HOCH

2

CH

2 NC cH cH H 2

CH

2 OHl Na O.,Na 180

SA

Thus, Sample A' was prepared. Furthermore, by following the same procedure as above while changing the stabilizer as shown in Table B below, Samples C', and G' were also prepared.

Table B Sample A' B' C' D' E' F' G' Stabilizer a-4 a-i IV-27 IV-45 IV-46 IV-47 The addition amount of each stabilizer was 10-4 04 4(1+i o mol/mol-Ag.

(a-4) (a-1) CHN N

OH

Same as a-i in Example 6 Also, by changing the Br content of the emulsions EM 5 and EM 6 for Layer 5 of sample E' (IVother samples were prepared.

A color developer having the composition shown below was placed in a beaker and allowed to stand for days at an opening rate of 0.08 cm- 1 and at room temperature 181

L

A t 4

B

Each of the color photographic papers (samples) was exposed through an optical wedge and processed as follows. The processed amount per day was 2.2 m 2 Replenisher Tank woor, a ri i i a Processing Step Temp. Time Amount Volume Color Development 380C 100 sec. 190 ml 17 liters Blix 330C 60 sec. 100 ml 9 liters Rinse 33°C 15 sec. 4 liters Rinse 330C 15 sec. 4 liters Rinse 33°C 15 sec. 200 ml 4 liters Drying 80 0 C 50 sec.

The amount of replenisher is m2 of the sample.

In addition, the rinse was performed by a 3 tank countercurrent system of from Rinse to Rinse The compositions of the processing solutions were as follows.

Colot Developer Tank Replenisher Water 800 ml 800 ml Diethylenetriaminepentaacetic 1.0 g 1.0 g Acid Nitrilotriacetic Acid 2.0 g 2.0 g 1-Hydroxyethylidene-l,1- 2.0 g 2.0 g diphosphonic Acid Benzyl Alcohol 16 ml 22 ml Diethylene Glycol 10 ml 10 ml Sodium Sulfite 2.0 g 2,8 g 182 bluish dye.

169 Potassium Bromide Potassium Carbonate Compound (Table 6) N-Ethyl-N- R-methanesulfonamidoethyl )-3-methyl-4aminoaniline sulfate Fluorescent Whitening Agent (WhitexO 4, made by Sumitomo Chemical Company, Ltd.) Triethylenediamine (1,4diazabicyclof 212,2)octane) Water to make pH (250 C) Blix Solution Water Ammonium Thiosulfate (70%) Ammronium Sulfite Ethylenediaminetetraacetic Acid Xron(111) Ammonium Disodium ethylenediaininetetraacetate Water to make pH (25 0

C)

Rinse Water 0.7 30 g 53 mmols, 5.9 g 1.5 g 5.0 g 1 liter 10.20 Tank F 400 ml 80 ml 24 g 30 g 5 g 1 liter 6.50 60 minols 8.0 g 2,0 g 5.0 g I liter 10.06 teplenisher 400 ml 95 ml 32 g 40 g 10 g 1 liter 6.00 Ion-exchanged water (content of caLcium and magnesium each being less than 3 ppia) was used.

After processing, the mkLnimum density (DmiIn) of cyan was measured. The results obtained~ are shown In -183

I

Table 6.

1841 f

O~

Table 6 Sample e.

Compound (I) 53 mmols/liter Br Content fM0l%) Compound (IV) so it It 1-7 ft Dmin Cyan 0.20 0.23 0.28 0.29 0.11 0.11 0.09 0.08 0.08 0.09 0.18 0.21 0.21 Comparison Invention

#I

If ComDarison

H'

1-28 1-44 Diethylhydroyxylamine ft I lL As is clear from the results shown in Table 6, it can be seen that according to this invention, good results are obtained and the effect by the using the compound of formula and the compound of formula (IV) is larger as the Br content is lower (Test Nos. 5 to 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 spirit and scope thereof.

alp.

186

Claims (12)

1. A process of processing a silver halide color photographic material, which comprises, after imagewise exposure, processing a silver halide color photographic material with a color developer containing an arcmatic primary amine color developing agent; and at least one of either a hydrazine or hydrazide represented by the following formula and either or both of at least one ccopound selected fromn monoamines represented by the following formula and condensed ring type amines represented by the following formula (III); 3 NN^ (I) R) wherein R 1 R2, and R3 each, independently, represents a hydrogen atom, an alkyl group, an aryl group, or a S; heterocyclic group; R4 represents a hydrogen atom, a -Ohydroxyl group, a hydrazino group, an alkyl group, an °aryl group, a heLerocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group; X1 Srepresents a divalent group; n represents 0 or 1, provided that when n is 0, R4 represents an altyl group, S an aryl group, or a heterocyclic group; and Ri and R 2 or R3 and R4 may form together a heterocyclic ring; and wherein R1, R 2 R 3 and R 4 aro optionally substituted; and 1 7 4S R 7 RS-N--R (1I) wherein RS, RG, R 7 each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group; and R 5 and Rs, RS and R7, or R 6 and R7 may combine with each other to form a nitrogen-containing heterocyclic ring; and wherein R' R and R7 are optionally substituted; and R8 N X2(III) R9 wherein X2 represents a trivalent atomic group necessary f...or completing a condensed ring; and R 8 and Rs, which -may be the same or different, each represents an alkylene group, an arylene group, an alkenylene groupr or an aralkylene group.

2. The p:ocess of processing a silver halide color photographic material as claimed in claim It 2 wherein the processing is performed in the presence of at least one o4 the compounds represented by formula (IV) 188 4) i Z-S-M (IV) wherein M represent a hydrogen atom, a cation, or -S-Z; and Z represents an optionally substituted heterocyclic residue containing at least one nitrogen atom.

3. The process of processing silver halide color photographic material as claimed in claim 1 or claim 2 wherein the silver halide color photographic material contains at least one of the compounds represented by formula (V) SR21 LltLL 3 2 2 N 00 NO N (V) (R 2 3 CH) 1 (R 2 4 -CH)m 2 I I X 4 CH 2 pl-Yl) s (Q 2 t2tXtCH2 )p 2 Y 2 2 Swherein R 21 and R22 each represents -C00R2 5 SR 2 6 S, "3R 5 or -CN, wherein R 25 and R 26 each represents a hydrogen atom, an alkyl group (optionally substituted) or an aryl group, R 23 and R24 each represents a hydrogen atom or an alkyl group; Q 1 and Q 2 each represents an aryl group; X4 and X5 each represents a bond or a divalent linkage group; Y 1 and y2 o a~each represents a sulfo group or a carboxyl group; Li, o 189 L2, and L3 each represents a methine group; ml, and m2 each represents 0, 1, or 2; n represents 0, 1, or 2, Pi and p2 each represents 0, 1, 2, 3, or 4; si and S2 each represents 1 or 2; and t. :Lnd t'2 represents 0 or 1, with the exclusion of the cases that ml, pl and t are simul- taneously 0 and that rm2, P2 and t-2 are simultaneously 0.

4. The process of processing a silver halide color photographic materii, as claimed in any one of claims 1-3 wherein the condensed ring type amine is a compound shown by following formula or (1-b) R 1 0 N--Rl--X 3 (l-a) P 12 3 10 1 wherein X represents -N or -CH, R and R have the same meanings as R 8 and R 9 in the formula (III) as claimed in claim 1 and R2 represents the group shown by R 0 and R 0f<" 0 0,s II or -CH 2 C-; 2{ 13 N/ 0 b) 0 R 14 0 1 wherein R 13 and R 14 have the same meanings as R 8 and P 9 in the formula (1Ii) as claimed in claim 1. The process of processing a silver halide color photographic material as claimed in any one of clans I to 4 whe,-ein the hydrazine or hydrazide represented by the formula is used 'in an amount of from 0.01 g to 50 g per liter of the color developer.

6. The process of processing a silver halide color photographic material as claimed in any one of claims 1 to 5 wherein the monoamine represented by the ±ormula and the condensed ring type amine represented by the formula (1X1) are used in an amzount of from 0.1 g to 50 a per ii'er of color developer.

7. The process o processing a silver halide color photographic material as claimed in any one of claims I to 6 wherein the silver halide is substantially composed of silver chloride.

8. The process of processing a silver halide color a a photographic material as claimed in any one of claims 1 to 7 wherein at a 0 6 0 o 3.9. 192 least one kind of cyan couplers shown by following formula (C-1) OH 33 31 R 33 NHCOR 3 1 R 32 11 wherein R 31 represents an alkyl group, a cycloalkyl group, an aryl group, an amino group, or a heterocyclic group; R 32 represents an acylamino group or an alkyl group having 2 or more carbon atoms; R 3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group; R 32 and R 3 3 may combine with each other to form a ring; and Z' 1 represents a hydrogen atom, a halogen atom or a group capable of being released at the reaction with the oxidation product of an aromatic primary amine color developing agent, is used.

9. The process as claimed in claim 8 wherein the amount of colour coupler is in the range of from 0.001 mol to I mol per mol of the light-sensitive silver halide in the silver halide emulsion, with from 0.01 mol to mol of a yellow coupler, from 0.003 mol to 0.3 mol of a magenta coupler, and from 0.002 mol to 0.3 mol of a cyan o coupler, per mol of the light-sensitive silver halide. The process of processing a silver halide color photographic material as claimed in any one of claims 1 0 to 9 wherein the temperature of the process is from 20 0 C to 50 0 C.

11. The process of claim 10 wherein the temperature is from 30 0 C co

12. The process of processing a silver halide color photographic material as claimed in any one of claims I 11 wherein the processing time is from 20 seconds to minutes. 0 42ll 9370AAM1 0.7.01 114 193

13. The process of claim 12 wherein the processing time is from 30 seconds to 2 minutes.

14. A process of processing silver halide color photographic material substantially as herein described with reference to any one of the Examples. Dated this 10th day of July 1991. FUJI PHOTO FILM CO., LTD By their Patent Attorney GRIFFITH HACK CO. 402/1 'OAA/10.7.01