JPS62168159A - Color image forming method - Google Patents

Abstract

PURPOSE:To make bleaching in a short period and to obtain a stable image density in a bleaching process by specifying the sum total of the dry film thickness of a total hydrophilic colloid layer on the side having a photosensitive layer to <=18mum. CONSTITUTION:Not only the image density by the fluctuation of bleaching conditions is stabilized but also the bleaching effect is synergistically accelerated when the multi-layered color photographic sensitive material having <=18mum sum total of the dry film thickness of the total hydrophilic colloid layer is subjected to the bleaching process in the presence of a bleaching accelerator. The sum total of the dry film thickness is <=18mum, more preferably 10-18mum, more particularly preferably 13-17mum. The method for forming a thin layer includes a method for decreasing the weight of the hydrophilic colloid which is a binder, method for using a coupler having high color formability, method for decreasing the weight of a high boiling point solvent, etc. The bleaching is thus quickly executed without environmental pollution and defective desilvering and the stable image density is obtd. in the bleaching process.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. Background of the Invention [Technical Field] The present invention relates to a color image forming method, and more particularly to a method for bleaching or bleach-fixing a color-developed silver halide color photographic light-sensitive material.

[Prior art and its problems]

In general, silver halide color photographic light-sensitive materials for photography include three types of light-sensitive layers: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer, a filter layer, an intermediate layer to prevent color turbidity, a halide prevention layer, a protective layer, etc. A non-photosensitive layer is provided on the support.

The dry film thickness of a silver halide color photographic light-sensitive material for ordinary photography (hereinafter abbreviated as color light-sensitive material for photography) is 20 to 30 micrometers (μm). Further, silver iodobromide is usually used as silver halide in the photosensitive layer of color sensitive materials for photography in order to increase photosensitivity and improve storage stability.

Furthermore, in recent years, non-photosensitive fine-grain halogens have been used to increase photosensitivity and to prevent inhibitory components from diffusing from the developer into the emulsion layer or from the emulsion layer into the developer during development to improve development stability. Silver oxide is used. It is known that this fine-grain silver halide has the disadvantage that it becomes difficult to be desilvered after development depending on its composition and amount.

In addition, in order to obtain a color image by developing a photographic color sensitive material that has been imagewise exposed, the metallic silver produced after the color development process is bleached with an oxidizing agent (bleaching agent), and then with a silver halide fixing agent. A fixing or bleach-fixing step is provided with a solution containing an oxidizing agent and a silver halide fixing agent.

Bleaching agents include blush liquid, ferric chloride, persulfate, etc., but these bleaching agents cause pollution, corrode the container, and have weak bleaching blades that take a very long time to bleach. It has the following disadvantages.

Compared to these bleaching agents, metal complexes of organic acids do not have any pollution drawbacks, and their weaker bleaching blades allow them to coexist with fixing agents such as thiosulfates, making them suitable for use in bleach-fix solutions. Not only can it be used, but it also has the advantage that it can be used repeatedly because it is regenerated by air oxidation. Therefore,
This metal complex of an organic acid has the advantage of simultaneously satisfying the problems of pollution, simplification of treatment steps, shortening of treatment time, and economic efficiency.

However, metal complexes of organic acids have relatively low oxidizing power, and bleaching solutions or bleach-fixing solutions using them as bleaching agents can be used for low-sensitivity silver halide color photographic light-sensitive materials, such as silver chlorobromide emulsions. When processing silver iodobromide, it has sufficient silver bleaching ability, but when processing color photographic materials containing silver iodobromide, the bleaching effect is insufficient and desilvering is insufficient. Development occurs. In particular, in the case of color photographic materials using fine-grain silver halide, desilvering defects are remarkable.

In order to solve this defective desilvering, techniques for using various bleach accelerators have been known, but among the known ones, the bleach accelerator described in Japanese Patent Application Laid-open No. 49 (1973) is known to have particularly excellent effects.
Aralkyl-substituted quaternary salts of alkylamines or aralkyl-substituted quaternary salts of nitrogen-containing heterocycles are known, as described in Japanese Patent No. 84440.

However, as a result of studies conducted by the present inventors, the problem with bleaching color photosensitive materials for photography in the presence of various bleaching accelerators is that not only is the bleaching accelerating effect insufficient, but also the bleaching conditions ( For example, the image density after development, bleaching, and fixing changes due to fluctuations in stirring conditions, temperature, time, organic acid metal complex concentration, etc., and there is a drawback that image density cannot be stably obtained. I found out.

Therefore, there is a strong need for a bleaching method that can bleach photographic color sensitive materials containing silver iodobromide as a main ingredient in a short period of time and that can provide stable image density even if the bleaching conditions vary.

■Object of the Invention Therefore, the first object of the present invention is to provide a color photosensitive material for photographing which can be bleached in a short time without causing environmental pollution or defective desilvering, and which can provide stable image density during bleaching processing. The purpose of the present invention is to provide an image forming method.

A second object of the present invention is to provide a method for forming a color image on a color photosensitive material for photographing, which allows stable image density to be obtained when processing with a processing solution having bleaching ability in the presence of a bleaching accelerator. It's true.

(2) Structure of the Invention The above-mentioned object of the present invention is to have a red-sensitive halogen northern limit emulsion layer containing a coupler, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer on a support, and to form a light-sensitive layer. The total dry film thickness of all the hydrophilic colloid layers on the side where
This is achieved by imagewise exposing a multilayer color photographic material having a size of .mu.m or less, color development processing, and then processing it with a processing solution having bleaching ability in the presence of a bleaching accelerator.

The present inventors have discovered that when bleaching a multilayer color photographic material in which the total dry film thickness of all hydrophilic colloid layers is 18 μm or less in the presence of a bleaching accelerator, the image density is only stabilized due to fluctuations in bleaching conditions. It has been found that the bleaching action is promoted synergistically.

■1 Specific structure of the invention The multilayer color photographic material (hereinafter referred to as color photographic material) which is advantageously used in the present invention has a total dry film thickness of layers formed on a support of 18 μm or less. The thickness is preferably 10-18 μm, more preferably 13-17 μm.

One method for thinning color photosensitive materials is to reduce the amount of hydrophilic colloid as a binder. The purpose is to retain minute coupler oil droplets etc. dissolved in silver halide and high boiling point solvent, to prevent fog increase due to FaFI & stress, and to prevent color turbidity due to diffusion of oxidized developing agent between layers. Since hydrophilic colloids are added to these materials, it is possible to reduce their weight within a range that does not impair their purpose.

Another method for thinning the layer is to use highly chromogenic couplers. Highly color-forming couplers advantageously used in the present invention include 2-equivalent couplers. For example, the 2-equivalent yellow couplers described in JP-A-52-15219 and JP-A-54-1233111, JP-A-53-123
129 and 5s-u8o34, 2-equivalent cyan couplers described in JP-A-53-105226 and JP-A-54-14736, etc. are used. Furthermore, examples of highly color-forming couplers that can be advantageously used in the present invention include polymer couplers. For example, Japanese Patent Publication No. 46-22513, U.S. Patent No. 3,
Polymer couplers described in US Pat. No. 767.412, US Pat.

Other methods for thinning the layer include reducing the amount of high-boiling solvent;
Examples include a method of thinning the intermediate layer by adding a scavenger of an oxidized developing agent to the intermediate layer between layers having different color sensitivities.

The effects of the present invention are particularly great when the color sensitive material for photography contains fine grain silver halide in the hydrophilic colloid layer. The average grain size of the fine grain silver halide is 0.03 to 0.30 μm, and it may be used in either the photosensitive layer or the non-photosensitive layer. The amount of fine grain silver halide used is usually 0.05g.
/ m2 (in terms of A g) to 0.7 g/m! However, the effects of the present invention will be more pronounced as the amount increases. As for the composition of the fine grain silver halide, silver chlorobromide, silver bromide, silver iodobromide, etc. are used.

The bleaching accelerator used in the present invention has the general formula CI) ~ [■]
It is indicated by.

General formula (1) General formula (II) “General formula (III) General formula [■] General formula i”
V) General formula (Vr) General formula [■] [In the above general formula, Q is a heterocycle containing one or more N atoms (
A represents an atomic group necessary to form a 5- to 6-membered unsaturated ring (including those in which at least one 5- to 6-membered unsaturated ring is condensed); (including B) in which at least one unsaturated ring is fused to this, B
represents an alkylene group having 1 to 6 carbon atoms, M represents a divalent metal atom, and X and X'' are =S, =O or =I
l't'', R'' is a hydrogen atom, and the number of carbon atoms is 1 to 6 g
Argyl group, cycloargyl group, aryl group, heterocyclic residue (if at least one unsaturated ring of 5 to 6 f"l is fused to this, it becomes a metal atom, ammonium group, amino group, nitrogen-containing ＼ R5 represents Z or an alkyl group, R1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue M (at least one 5- to 6-membered unsaturated ring
R'Jt', R', R', R and R' each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, It represents a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. However, R4 and R5
may represent -B-SZ, and R, R', I't
'' and R3, R4 and R5 may be cyclized with each other to form a heterocyclic residue (including one in which at least one 5-6H unsaturated ring is fused thereto).

R'' and R' represent each, R9 is an alkyl group or -(CH2)n5sOs
However, when RIB is -(C1l-)n-3Oa'', σ represents 0 or l. ) G is an anion, lll
+ to m4 and nl to R8 each represent an integer of 1 to 6, and m represents an integer of 0 to 6. R8 is a hydrogen atom or an alkali metal atom, provided that Q' has the same meaning as Q above. D
represents a simple bond, an alkylene group or vinylene group having 1 to 8 monoprimes, and q represents an integer of 1 to 10. A plurality of D's may be the same or different, and the ring formed together with the sulfur atom may be further fused with a 5- to 6-membered unsaturated ring. X
' is -COOM', -OH, -303M'.

C0NHz, 5OJHt, NHt, SH,
CN, C0tR”.

-3o, RIB, -OR+@, -NR1''RI7.
-3R", -SO,R".

-NlICOR", -NH30,R1", -0CO
RI" or -8O2R", Y' represents or a hydrogen atom, and m and n each represent an integer of 1 to 10. Rl l, RIB, RI4. R", R"
and RIll is a hydrogen atom, a lower alkyl group, an acyl group, or -('C)-X' 1 @R'! and RIB represents a lower alkyl group. R” is -N
R"R", -OR" or -5R12, R" and R
” represents a hydrogen atom or a lower alkyl group, R22 is R
Represents an atomic group necessary to connect with I8 to form a ring.

R'' or R21 and R18 may be connected to form a ring.M' represents a hydrogen atom or a cation.The compounds represented by the above general formulas C11 to [V] may be enolized or Contains salt.] General formula [■] In the formula, R" to R" are -OR" and -3R".

represents an alkyl group having as a substituent, R" to R" represent a hydrogen atom or an alkyl group, and R2g and R", R"
and R3'' and R33 and R'' may combine to form a heterocycle with a nitrogen atom, Y represents a 2 lit organic group, X represents an ion, and X and y each represent O or 1 and Z is 0, 1.2.3 or 4.

The alkyl group represented by R13 to R'' includes the above-mentioned substituents 1OR'' and -3R''.

It is preferable that the straight chain portion connecting the nitrogen atom to which R13 to R'' is bonded has 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.Also, R23 and R25, R24 and R'' are each Preferably they are the same group.

The alkyl group represented by R13~R'' may be linear or branched, and may have a substituent other than the above substituents.The alkyl group represented by R''~R'' has a carbon atom number 1 to 5 is preferable, and a substituent may be present.

]:j The heterocycle which may be formed with a nitrogen atom by bonding 211 and R'', R'' and R'', or R'' and R'' may be saturated or unsaturated, preferably 5 ~7-membered, specific examples include piperidine ring and morpholine ring. Specific examples of the alkyl group represented by R13~R'' in R''~R'' include the following.

-C)l, C)1. OH -CH2Cl, CHffiOH -CH,CH,0CH3 -CH,OH -CHffiCH! 5l ( -CIi, CH25CH.

CHICHHzOC*Hs -CH,CH,SC,1(8 -CH,CH25HI CH25HJ (CHs) * -C1,C0NH.

Preferred divalent organic groups represented by CH2CHtCON(CHs) z -C1,C3N(CJ,) I CHri-CHCHtOH Y include alkylene, arylene, cycloalkylene, heterocyclic groups, and these groups. or more directly or 10-,-S
, -Sow-, -Go-, -NR35 (R35 represents a hydrogen atom, an alkyl group or an aryl group), -C
ONR” - (R” is synonymous with R”) or 2SO□N
Examples include those bonded via H-.

The alkylene preferably has 1 to 1 carbon atoms.
Preferred arylenes include phenylene and naphthalene, and preferred cycloalkylenes include 5- to 7-membered arylenes.

The heterocycle may or may not be aromatic.

Examples of the heterocycle include a tetrahydrofuran ring.

The above divalent organic group may have a substituent, and examples of the substituent include halogen, alkyl, hydroxy, alkoxy, -COOM', -So, tM''(M' and M2 are acids, salts, or esters). ), sulfonamide, sulfamoyl, carbonamide, carbamoyl, and p is 0 or I) are preferred.

Particularly preferred among Y2 are -CI in the general formula,
-The terminal portion bonded to the group is -alkylene-aromatic ring group-
(alkylene moiety bonds with -Cfly-) or -
It is an aromatic ring group.

Specific examples of the divalent organic group represented by Y include the following.

The ion represented by X2 is an ion for balancing the charge of the compound of the general formula, and can be either a negative ion or a positive ion.

Examples of negative ions include halogen ions, carboxylate ions, sulfonate ions, and nitrate ions, and examples of positive ions include alkali metal ions and ammonium ions.

The bleaching accelerator of the present invention is represented by the general formulas (1) to [■], and typical examples thereof include, but are not limited to, the following.

[Exemplary compounds]

(I-1) (I-2)C
If, COO1(CI+□(CIf2)3COOII(
1-15) (I-1
6) (I-17) (1
-18) (I -21)
(1-22) (r -23)
(I-24) ([-27)
(r -28) (I -29)
(I-30) (1-31)
(I-32) (I-33)
(1-34) (I-37)
(1-38) (II-1)
(n-2) (n-3)
(n-4) (II-5)
(n-6) (n-7)
(If-8) (n-9)
(n −10)(II, −tD
(II-(2)(II-13)
(n -14) (n -15)
(II-16) (II-1
7) (n -18) (n
-19) (ll-20) (n-21) (II -22) (n -23) (U -24) (I[-25) (II -26) (n -27) (n -28) H , N-C5NHNHCS-Nut (II -29) (If -30) (ll-31) (I[-32) (n -33) (n -34) H, N-C3NH (CH,), NHC3-NHt (n
-35) HzN C5NH(CH2)4NHC3NH2(n
-36) H2N-C3NI((CH2)JHCS-NH2(II
-37) ([1-38) (II-39) (n -40) (II -41) (ll-42) (n -43) (n -44) (If -45) (II-46) ( n -47) (ll-48) 3 b (II -49) (n -50) (n -51) (■-52) (II -53) (n -54) (II -55) (n-56 ) (II-57) (II -58) (n -59) (II -60) (n -61) (II -62) (n -63) (n -64) (n -65) HJ CS S CNHt ll II S (n -67) (n -68) II Na Na (n -69) (n -70) (II-71) (n -72) (I[-73) (ll-74) (n -75) (n -76) (II -77) (II -78) (n -79) (I[-80) (■-81) (■-82) (n -83) (II -84) ( n -85) (n -88) (II -87) (II-88) (II -89) (ll-90) ■ (II -91) (I[-92) (II -94) (n -95 ) (II -97) (II -99) (II -100) (n -1ot) (n -102) (n -103) (II-104) (n -105) (n -106) (n -107 ) (n -109) υ (n-110) (II -111) (n
-112) (ll-115)
(n -116) (II -117)
(II-u8) (II-119)
(n -120) (ll-125)
(I[-126)(II-12
7) (II-128) (n
-131) (n -132)
(ll-135) (n −
136) (If -137) (
II-138) (II-139)
(II-140) (II-141)
(n -142) (II-143) (II -144) (n -145) H (n -146) H (n -147) H (II-148) (n-149) (II-150) (n -151) (n -152) (II-153) (II-154) (If-155) (I[-156) υ (n-157) (n -158) (II[-1) ■2N CHtCHt SH ([[-3) (III-4) (III-5) HOOC-CH2Cl+2・5R (I[l-6) (III-7) (III-8) (I[[-9
)(III-10) (I[[-11) (II[-12) (II[-13) H3 (III-14) (I[l-15) (III-16) (II[-17) (I[l-18) (II[-19) CIlzCHt Sit ■ ([[-20) (II[-21) (III-
21) C1,CH,-5H (I[[-23) (I[
I-24) (III-25)
(In-26) (III -27) CH (rff-28) (I[[-29) (I
II-30) (I-31)
(I-32) (III-33) (In-44) (II[-35) (I[I-36) (III-37) (1'i'-1) CH3H3 (■-2). H3■ (IV-3) (#-4) (IV-5) CHa(V-
1) (V-2)N −
N
To N□ (V-3) (
V-4) (V-7) (
V-8) (V-9)
(V-10) (V-11)
(V-12) srl
[Jtl(V-
17) (V-18)
(V-19) (V-
20) (V-21) (
V-22) (V-23)
(V-24) (V-31)
(V-32) (V-33)
(V-34) (V-35)
(V-36) (V-40
) (V-41) (V-43) (V-44
) (V-45) (V-46
)(V-51) (V-5
2) (V -53) (V
-54) (V -57)
(V-58) (V-59)
(V-60) (V-61)
(V-62) (V-63)
(V-64) (V-65)
(V-66) (V-67)
(V-68) (V-69)
(V-70) (V-7
1) (V -72) (V-
73) (V -74) (V
-75) (V -76
) (V-77) (V-7
8) (V-79) ' (V
-80) (V -81) (V
-82) (V -43) (V
-84) (V -85)
(V-86) (V-87)
(V-88) (V-89)
(V-90) (V-91)
(V-92) (V-93) (V~94) (V -95) (V-96
) (V −97) (V −
98) (V -99) (V-
100) (V-101) (V
-102) (v-103) (
V-104) (V-105) (
V-106) (V-107) H2 (V-108) (V-110) (V-111) bυsNa bU3Na (V-114) (V-116) (V-118) (V-119) (V- 120) (V-121) (V-123) (V-1
24) (V-125) (V
-126) (V-127)
(V-128) (V-131)
(V-132) bli
SR (V-133)
(V-134) (V-139
) (V-140) (V-
141) (V-142)
(V-143) (V-1
44) (V-145) (V
-146) (V -147)
(V-14111) (V-149)
(V-150) (V-151)
(V-152) (V-153)
(V-154)I (V-155) (V-
156) q■ (V-157) (V -
158) (V-159)
(V-160)H (V-161) (V-1
62) t12 (V -163) (V-
164) (V-165)
(V-166) Sl'1 (V-167) (V-1
68) (V-189)
(V-170) (V-173) (V
-174) (V-175) (V-176
) (V -177)(
V-178) (V-179)(
V-180) (V-
181) (V-182)
(V-183) 5tl
5tl (V-184) H (VI-1) (VI-2)
(Vl-3) (VI-4)
(W-5) (VI-6) (VI
-7) (VI -8) (V[-11)
(VI-12) ' (Vl
-13) (Vl-14) (VI-15)
(VI-16) (Vl-17)
(VI-18) (■-19)
(VI-20) (Vl-21)
(VI-22) (Vl-23)
(V[-24) (VI-25) (VI
-26) (VI-27)
(Vl-28) (Vl-29)
(W-30) (VI-31) (Vt
-32) (W-33)
(Vl-34) (VI-35)
(Vl-36) (■-5) (vlI-6)oH (■-8) (■-9) Shi113 (■-10) (■-11) (■-12) (■-13) CH3 ( ■-17) HSCH,NHCH,CH,OH (■-18) HSCH,CH,NCH,CH,O
HC2H.

(■-19) H3CH2CH2NCH2CHJ
(CH3)! CH.

(■-20) H3C11□CHtNCHtCHtOC)1. cIIt
OcH.

C0CH.

HJ (L; l'12L; th5) 1 no 2 (■-7) (X pieces-8) (■-10) (HOCH1CH2)2NCH2CH,0CH2CH2
N(CH2Cl,0H)2(■-11) (■-12) (■-16) (■-27) S
b (■-28) (■-29) (■-30) (■-32) (■-34) (■-35) CQe (■-36) (■-37) (■-38) (■- 39) CQ0 (■-40) (■-41) CH3(iH3 (■-42) (■-43) (■-44) (CHASCHtCHt)JCH2CHtOCHtCH
J(CH3CHtCHt)2(■-45) (■-46) (CH30CHtCHt) 2 N(CHI) , 30
(CHt) 3 N (C112CH, 0C113) 2
(■-47) (HSCH3CH2)2N(CH2)8N(C12CH
2SH)! (■-48) (■-49) (■-50) The above compounds are, for example, British Patent No. 1.138,842,
JP 52-20832, JP 53-28426, JP 53-95630, JP 53-104232, JP 53
-141632, 55-17123, 60-9
5540, U.S. Patent No. 3,232°936, U.S. Patent No. 3,7
No. 72,020, No. 3,779,757, No. 3,89
It can be easily synthesized using known techniques such as those described in No. 3°858.

The bleaching accelerator of the present invention only needs to be present when bleaching the silver image obtained by the phenomenon, and is preferably added to a bleaching bath or a bleach-fixing bath. It is also preferable to add the compound to the silver halide color photographic light-sensitive material (pretreatment solution) and incorporate it into the bleach bath or bleach-fix bath. In this case, a method may be used in which the silver halide color photographic material is preliminarily contained in the silver halide color photographic light-sensitive material at the time of production, and then made to be present during processing in a bleach bath or bleach-fix bath.

These bleach accelerators of the present invention may be used alone or in combination.
More than one species may be used in combination, and the amount of the bleach accelerator added to the bleach-fix solution is generally about 0.01 per tC of processing solution.
Good results are obtained in the range of −100 g. however,
In general, if the amount added is too small, the effect of promoting bleaching will be small, and if the amount added is too large, precipitation may occur and contaminate the silver halide color photographic material being processed. 0.05 to 50 g is preferable, and more preferably 0.05 to 50 g per 1e of treatment liquid.
It is 15g.

When adding the bleach accelerator of the present invention to a bleach bath or a bleach-fixing bath, it may be added and dissolved as is, but it is generally added after being dissolved in water, an alkali, an organic acid, etc. If necessary, it may be dissolved in an organic solvent such as methanol, ethanol, acetone, etc. and added, without any effect on the bleaching accelerating effect.

When the bleach accelerator of the present invention is contained in a multilayer silver halide color photographic light-sensitive material, the photographic constituent layers include:
Silver halide emulsion layers and/or their adjacent layers are preferred.

When the compound is added to the photographic constituent layer, the amount added is l x 10-5 to 5 x 10-' mol/
A range of m 2 is preferred, with t x to-' to t x
More preferably 10-3 mol/m2.

Examples of the processing liquid having bleaching ability include a bleach-fixing liquid and a bleaching liquid.

As the bleaching agent used in the processing solution having bleaching ability, metal complex salts of organic acids are preferred.

Cobalt is preferred, and ferric ions are particularly preferred.
.

The organic acid is preferably a polyvalent (preferably di- to tetravalent) carboxylic acid, and a particularly preferred organic acid is, for example, a 7-minopolycarboxylic acid represented by the following general formula (IX) or (X).

General formula (IX) II OOC-^1-Z-^2-COO11 General formula (X
) In each of the above general formulas, A , , A 2. A,,A,,A
S and A6 each represent a substituted or unsubstituted iX hydrogen group, and Z represents a hydrocarbon group, an oxygen atom, a sulfur atom, or >N-A7 (A? is a lower fatty acid carboxylic acid, which is a hydrocarbon group).

These 7 minoboricarboxylic acids are alkali metal salts, ammonium salts, or water-soluble amino/salts. Representative examples of aminopolycarboxylic acids or other aminopolycarboxylic acids include the following. can.

ethylenenoaminethitraacetic acid diethylenetriaminepentaacetic acid Ethylenediamine-N-(β-oxyethyl)-N.

N',N'-Triacetic acid propylenenoaminetitraacetic acidnitrotriacetic acidcyclohexanediaminetetraacetic acidiminoacetic aciddihydroxyethylglycine ethyl etherdiaminetetraacetic acid glycol ether diaminetetraacetic acidethylenenoaminetetrabrobionic acidphenylenediaminetetraacetic acidethylenediaminetetraacetic acid disodium Salt Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt Ethylenediaminetetraacetic acid tetrasodium salt Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N-(β-oxyneethyl: l-N.

N',N'-Triacetic acid sodium salt Propylene diamine tetraacetic acid sodium salt Nitrilotriacetic acid sodium salt Chlohexanediamine tetraacetic acid sodium salt The amount of the metal complex salt of the above organic acid used is 5 to 400 g per processing liquid IQ having bleaching ability. is preferable, especially 10 to 200
g is preferred.

Additives that can be used in the bleach solution include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, among others.

I) H such as borates, acid salts, acetates, carbonates, phosphates, etc.
Buffers, salts of aminopolycarboxylic acids, alkylamines, polyethylene oxides, and other substances known to be added to bleaching solutions can be appropriately added.

In the present invention, when the bleaching step is carried out using a bleach-fix solution, the bleach-fix solution may contain a metal complex salt of an organic acid (for example, an iron complex salt) as a bleaching agent, as well as a thiosulfate or a thiocyanate. A liquid having a composition containing a silver halide fixing agent such as , thioureas or the like is applied. In addition, a bleach-fixing solution comprising a bleaching agent and the above-mentioned silver halide fixing agent, as well as a small amount of a halogen compound such as potassium bromide;
Alternatively, there are also bleach-fix solutions with a composition containing a large amount of halogen compounds such as potassium bromide, and even special bleach-fix solutions with a composition consisting of a combination of bleach and a large amount of halogen compounds such as potassium bromide. Can be used.

As the halogen compound, in addition to potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, ammonium iodide, etc. can also be used.

The silver halide fixing agent to be included in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. thiocyanates such as thiosulfates, potassium thiocyanate, sodium thioneanate, ammonium thiocyanate, or thioureas, thioethers, high concentrations of bromides,
Iodide is a typical example.

The bleach-fix solution contains boric acid, borax, and
Sodium hydroxide, potassium hydroxide, sodium carbonate,
pH buffering agents consisting of various salts such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxyamine, hydranone, and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, or stabilizers such as nitroalcohol nitrates, methanol, trimethylformamide, dimethyl sulfate, etc. An organic solvent such as Okinodo may be appropriately contained.

The I)H of the bleaching solution is 20 or more, but generally it is 4.
．． 0 to 9.5, preferably 4.5 to 80, most preferably 5.0 to 70.

The pH of the bleach-fix solution is used at 4.0 or higher, but it is generally used at a pH of 5.0 to 9.5, preferably 60 to 8.5.
most preferably from 6.5 to 85.

Silver halide emulsions used in the photographic color sensitive material of the present invention include silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiobromide, and silver chloride. Any emulsion commonly used in silver halide emulsions can be used, but silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or the other may be mixed during the night when either one is present. Alternatively, halide ions and silver ions may be generated by sequentially and simultaneously adding the halide ions and silver ions while controlling the pHlPAg in the mixing pot, taking into consideration the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of AgX to change the halogen composition of the particles.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains.

Silver halide grains are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (
Metal ions can be added using at least one selected from iron salts (including complex salts) and iron salts (including complex salts) to contain these metal elements inside the particles and/or on the particle surfaces. By placing the particles in a reducing atmosphere, reduction-sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, use Research Disc.
It can be carried out based on the method described in Section 2 of No. 17643 (hereinafter abbreviated as RD).

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of (100) and (111) planes can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of silver halide grains is 0.05~
30μ, preferably 0.1 to 207t can be used.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). When divided by the average grain size, the value is 0.20 or less.The grain size is the diameter in the case of spherical silver halide, and the projection of the value in the case of grains with shapes other than spherical. This indicates the diameter when the image is converted into a circular image of the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsions may be formed separately and two or more types of silver halide emulsions may be mixed and used.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that does not itself have a spectral sensitizing effect, or a super sensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. It's okay.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex melonanine dyes, holobolanoine dyes, heminanine dyes, steryl dyes, and hemioxanol dyes are used.

Particularly useful pigments include cyanine pigments, melonanine pigments,
and a complex merocyanine pigment.

Silver halide emulsions are used during chemical ripening, at the end of chemical ripening, and/or for the purpose of preventing fog during the material manufacturing process, storage, or photographic processing, or to maintain stable photographic performance. After completion of chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsions
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

Photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using silver halide emulsions are made by using one or more hardeners to crosslink binder (or protective colloid) molecules and increase film strength. Can be hardened.

The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

For example, aldehydes (formaldehyde, glyoxal, retail aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-nohydroquine dioxane, etc.), activated hinyl compounds (+ , 3.5-
Triacryloyl-hexahydro-S-trianone, 1
．． 3-vinylsulfonyl-2-propatur, etc.), active halogen compounds (2,li-dichloro-6-hydroxy-8-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoquine chloric acid, etc.), etc. alone. Or they can be used in combination.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, section 2, A.

In photosensitive photographic emulsions, distillates, and other water-based colloid layers, dispersions (latex) of water-insoluble or sparingly soluble synthetic polymers can be contained for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or together with acrylic acid, methacrylate Polymers with combined monomer components such as acids, α, β-unsaturated dicarboxylic acids, hydroquine alkyl (meth)acrylates, sulfoalkyl (meth)acrylates, styrene sulfonic acids, etc. can be used.

The emulsion layer of the light-sensitive material contains a dye-forming compound that undergoes a campling reaction with an oxidized product of an aromatic primary absorbing amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) to form a dye during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer; A magenta dye-forming coupler is used in the sensitive emulsion layer, and a dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful fragments such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included.

Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIfl coupler, a DIR compound may be used which undergoes a Camplink reaction with the oxidized form of the main agent to produce a colorless compound and at the same time releases a development inhibitor.

The DIR couplers and DIR compounds used include those with an inhibitor attached directly to the coupling position and those with an inhibitor attached directly to the coupling position.
It is bonded to the coupling position via a valence group, and is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle separated by the coupling reaction ( (referred to as timing DIR couplers and timing DIR compounds). Moreover, one that is dispersible after release from the inhibitor and one that is not so dispersible can be used alone or in combination depending on the purpose. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include, for example, U.S. Patent No. 2.87.
No. 5,057, No. 3,265.506, No. 3,4
No. 08,194, No. 3,551,155, No. 3,
No. 582,322, No. 3,725,072, No. 3
, 891°445, West German Patent No. 1,547,868,
West German Application No. 2,219.917, No. 2,261,3
No. 61, No. 2,414,006, British Patent No. 1,42
No. 5,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 1977
-26133, 48-73147, 50-63
No. 41, No. 50-87650, No. 50-123342
No. 50-130442, No. 5I-21827,
No. 51-102636, No. 52-82424, No. 5
It is described in No. 2-115219, No. 58-95346, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat. No. 2,600,788, U.S. Pat.
No. 3,311,476, No. 3,419,39
No. 1, No. 3.519,429, No. 3.558, 3
No. 19, No. 3,582,322, No. 3,615.
No. 506, No. 3,834,908, No. 3,891
．． 445, West German Patent Application No. 1°810.464, West German Patent Application (OLS) No. 2,408,665, West German Patent Application No. 2°417.
No. 945, No. 2,418,959, No. 2,424,4
No. 67, JP 40-6031, JP 49-740
No. 27, No. 49-74028, No. 49-129538
No. 50-60233, No. 50-159336,
No. 51-20828, No. 51-26541, No. 52
-42121, 52-58922, 53-55
No. 122, Japanese Patent Application No. 110943/1980, and the like.

Phenol or naphthol couplers are generally used as dye-forming couplers.

Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Pat.
2゜801.171, 2,895.826, 3,476.563, 3,737,326
No. 3,758.308, No. 3.893゜04
Specification No. 4, JP-A-47-37425, JP-A No. 50-10
No. 135, No. 50-25228, No. 50-11203
No. 8, No. 50-117422, No. 50-130441
Those described in publications, etc., and those described in Japanese Patent Application Laid-Open No. 58-987
The couplers described in Publication No. 31 are preferred.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°.
A high boiling point organic solvent of C or higher, if necessary, a low boiling point, and/or
Or, by dissolving it in combination with a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, float mixer, or ultrasonic device, After being emulsified and dispersed, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling point solvents include phenol derivatives, phthalate alkyl esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, etc. that do not react with the oxidized form of the developing agent. Organic solvents are used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. It can also be incorporated into hydrophilic colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants are used. be able to.

The oxidized product or electron transfer agent of the main agent moves between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color blurring or deterioration of sharpness. A color antifoggant may be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself,
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Preferably used compounds that can be used with 2 are those described in RD 17643, section 2, J.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. A compound that can be preferably used as a development accelerator is RD 17
The compound is a compound described in Section B-D of Section XX1 of No. 643, and the development retardant is a compound described in Section E of Section XXI of No. 17643. A black and white developing agent and/or its precursor may be used for development acceleration and other purposes.

The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea derivatives, imidazole derivatives, and the like.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiilanoation layer, and the like. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during development. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anionine dyes, and azo dyes.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material can be used to reduce the gloss of the light-sensitive material, improve the ease of writing,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other.

Any matting agent can be used, such as silicon dioxide, titanium dioxide, magnesium dioxide,
Examples include aluminum dioxide, notrium sulfate, carunium carbonate, acrylic acid and methacrylic acid polymers and their esters, polyhinyl resin, polycarbonate, and styrene polymers and copolymers thereof.

The particle size of the cloak agent is preferably 0.05 μ to 10 μ. The amount added is preferably 1 to 300 mg/m''.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used in the emulsion layer and/or the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 X■.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be coated with coating properties, antistatic properties, slipperiness properties, emulsification dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (development acceleration, film hardening, sensitization, etc.).

The support used in the photosensitive material of the present invention includes paper laminated with an α-olefin polymer (e.g., polyethylene, polypropylene, ethylene/butene copolymer), etc.
Flexible reflective supports such as synthetic paper, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and reflective layers on these films. flexible support provided with glass, metal,
Includes pottery etc.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be applied through one or more subbing layers to improve antihalation properties, friction properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As a coating method, extra-noyon coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, or packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of the surfactant include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glinodol, higher argylamines, quaternary ammonium salts, pyrinone, and other complexes. rings, cationic surfactants such as phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
U anionic surfactants containing acidic groups such as phosphoric acid, sulfuric acid esters, and phosphoric acid esters; amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or polydiacid esters of amino alcohols. good.

Furthermore, it is possible to use a fluorine-containing surfactant for the same purpose.

To obtain a dye image using the method of the present invention, exposure is followed by color photographic processing. Color processing is a color development process,
A bleaching process, a fixing process, a washing process, and, if necessary, a stabilizing process are performed, but instead of the process using a bleaching solution and the process using a fixing solution, a warm white fixer is used. It is also possible to carry out the bleach-fixing process using
In combination with these processing steps, a surface hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development treatment step, an activator treatment step may be performed in which a color developing agent or its precursor is contained in the material and the development treatment is performed using an activator solution. During these processes,
Typical processing is shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process or a stabilization process.) - Color development process - bleaching process - constant fixation process - color development process - bleach-fixing process Process - Anti-sand film treatment process - Color development treatment process - Stop fixing treatment process - Water washing treatment process - Bleaching treatment process Constant coloring treatment process - Water washing treatment process - Post-hardening treatment process - Color development treatment process - Water washing treatment process - Supplementary color development Development process - Stop process - Bleach process Constant fixation process/Activator process - Bleach-fix process/Activator process - Bleach process Constant fixation process Processing temperature is usually 10°C to 65°C. Although the temperature is selected within the range, the temperature may exceed 65°C. Preferably 25
Processed between °C and 45 °C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylenediamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids; for example, salt-like acids, sulfates, p-toluenesulfonates, sulfites, sulfates, benzenesulfonates, etc. can be used. can.

These compounds are generally about 0.0% in color developer tQ.
A concentration of 1 to 30 g is used, more preferably a concentration of about 1 to 15 g for color developer IQ.

If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

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

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted.

Among them, examples of particularly useful compounds include N,N-methyl-p-phenylenediamine hydrochloride, N-medyl-p
-phenylenenoamine hydrochloride, N,N-dimethyl-p-
Phenyldiamine hydrochloride, 2-amino-5-(N-ethyl-N-dodenylamine)-toluene, N-ethyl-
N-β-methanesulfonamidoethyl-3-methyl-4
-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-
N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p
-Toluenesulfonate, etc. can be mentioned.

Further, the above coloring agent may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (actihator solution) instead of the color development liquid, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It can also contain various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as nthrazine, and preservatives such as hydroxylamine or sulfites. It's okay.

Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfokide can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or hexose, pyrogallol-1,
3-dimethyl ether etc. may be contained.

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and noethylenetriaminopentaacetic acid, l
-organic phosphonic acids such as hydroquinoethylidene-1,1'-enephosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethyleneaminetetraphosphoric acid, oxocarboxylic acids such as citric acid or glyconic acid, 2- Examples include phosphonocarboxylic acids such as phosphonobutane 1.2.4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

A fixer having a commonly used composition can be used. As fixing agents, compounds that react with silver halide to form water-soluble complex salts, such as those used in ordinary fixing processes, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, and potassium thionoanate are used. Typical examples include thiocyanates such as sodium thiocyanate and ammonium thionoanate, thioureas, and thioethers. These fixatives are 5
It is used in an amount that can be dissolved at 9/e or more, but it is generally used in an amount of 70 to 2509/Q. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

In addition, various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be used alone or in the fixing solution. 2
It can be contained in combination of more than one species. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydranone, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, hardening agents such as water-soluble aluminum salts, Organic solvents such as methanol, dimethylsulfamide, dimethylsulfokide, etc. can be contained as appropriate.

The pH of the fixer is used at 3.0 or higher, or is generally used at pH 3.0 or higher.
H4, used in the range of 5 to 10, preferably 5 to 9.5, most preferably 6 to 9.

[Example (1)] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all the examples below, the amount added in the silver halide photographic material is based on In2 unless otherwise specified.

In addition, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample = 1 (comparison) 1st layer; antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Dry film thickness: 3 μm Second layer; Intermediate layer (1, L,) Gelatin layer containing an emulsified dispersion of 2.5-not-t-octylhydroquinone.

Dry film thickness 1.0 μm 3rd layer, low sensitivity red-sensitive silver halide emulsion layer (RL-1)
Monodisperse emulsion (emulsion l) consisting of AgBr I with an average grain size (r) of 0.30 μm and containing 6 mol % of Ag1...Silver coating amount 1.8 g/m" Sensitizing dye I - 6 per mol of silver X 10-' molar sensitizing dye■...
- OX 10-5 mole cyan coupler (C-1) per mole of silver Colored cyan coupler (CC-1): 0.06 mole per mole of silver 0.003 mol DIR compound (D-1)... 0.0015 mol per mol of silver DIR compound (D-2)... 0.002 mol per mol of silver Dry film thickness 3.5 μm 4th layer: High sensitivity red-sensitive silver halide emulsion layer (RH-1)
It is made of AgBrl with an average particle size (r) of 0.5 μm and 17.0 mol% of Ag.

Monodispersed emulsion (emulsion ■)... Silver coating amount 1.3 g/m' sensitizing dye 1. 3 x 10-5 moles of sensitizing dye ■ for 1 mole of silver...
- t, ox per mole of silver 1o-5 moles cyan coupler (C-1) 0.02 moles per mole of silver color ton uncoupler (CC-1)...0 per mole of silver .0 (115 mol DIR compound (D -2)... 0.001 mol per mol of silver Dry film thickness 2.5 μm 5th layer; Intermediate layer (1, L,) Same as 2nd layer, gelatin layer.

Dry film thickness 1.0 μm 6th layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1)
Emulsion -■...Coated silver M1.5g/m2 Sensitized color code■
... 2.5X 10-5 mole increase per mole of silver island dye■
... 1,2X 10-S mole magenta coupler (M-1) per mole of silver... 0.050 mole colored magenta coupler (CM-1>...silver 1 0.009 mole per mole) I R compound (D-1)... CO per mole of silver, 0010 mole 1) r R compound (D-1)... per mole of silver 0.0030 mol*7. Dry film thickness: 3.5μIII 7th layer; high-sensitivity green-sensitive silver halide emulsion) j'i (nill-1) 7L Sharpening = II-...Coated silver Mt 1
, 41 (/+n' sensitizing dye 1 ■... C1,5X 10-5 mol sensitizing dye ■ for 1 mol of silver
... @ t, ox + o pmol magenta coupler (M-1) for 1 mole of silver... 0.020 mole for 1 mole of silver Colored magenta coupler (CM-1)... for 1 mole of silver 0.002 mol DIR compound (D-3)... 0.0010 mol per mol silver Dry film thickness 2.5 μm 8th layer: Yellow filter single layer (YC-1) Yellow colloidal silver and 2. a gelatin layer comprising an emulsified dispersion of 5-di-t-octylhydroquinone.

Dry film thickness 1.2 μm 9th layer; low sensitivity blue-sensitive silver halide emulsion layer (BL-1)
CAgBr with average particle size of 0.48 μm and containing 16 mol% of Ag
Monodisperse emulsion consisting of I (emulsion ■)...silver coating ff10.9g/m
2 Sensitizing dye ■...J, 3Xlo-5 moles per mole of silver Yellow coupler (Y-1le...0.29 moles per mole of silver Dry film thickness 3.5μm 10th layer: High Sensitivity Blue-sensitive emulsion layer (BH-1) Average grain size 0
．． AgBr l containing 8 μIn, 15 mol% Agl
Monodispersed emulsion (emulsion ①) consisting of silver coating lO, 5 g/m' sensitizing dye ②... 1.0% per mole of silver. OX 10"" mol Yellow coupler (Y-1)... 0.08 mol per mol of silver DIR compound (D-2)... 0.0015 mol per mol of silver Dry film thickness 2. 5 μm 11th layer; 1st protective layer (Pro-1) Silver iodobromide (Ag 14 mol% average grain size 0.07 μm)...
・Silver coating amount 0.5 g/m' Gelatin layer containing ultraviolet absorbers UV-1 and UV-2 Dry film thickness 2.0 μm 12th layer; 2nd protective layer (Pro-2) Polymethyl methacrylate particles (diameter 1 Gelatin layer containing formalin scavenger (HS-1) and formalin scavenger (HS-1) dry film thickness 15 μm In addition to the above composition, each layer contains a gelatin hardening agent (H-1
) and surfactants were added.

Further, the dry film thickness of each layer was adjusted according to the amount of gelatin so that the film thickness was as described above.

The dry film thickness was measured using a commercially available contact type film thickness meter at 23°C.
The measurement was performed after the sample was conditioned to 55% RH for 24 hours or more.

The total dry film thickness of sample 1 is 277 μm.

The compounds contained in each layer of sample 1 are as follows.

Sensitizing dye I; anhydro-5,5'-dichloro-9-ethyl-3,3'-no(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■; anhydro-9-ethyl-3,3'- Di(3-sulfopropyl)-4,5゜4',5'-dibenzothialopocyanine hydroquine sensitizing dye ■; anhydro-5,5'-diphenyl-9-
Ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye ■; anhydro-9-ethyl-3,3'-di(3-sulfopropyl)-5,6,5'.

6'-dibenzoxacarbonanine hydroxide sensitizing dye ■: Anhydro 3.3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine D-3 01+ l V-2 Next As shown in Table 1, Samples 2 to 6 were prepared by reducing the amount of gelatin in Sample 1 in the same ratio for each layer.

After each sample No. 1 to 6 prepared in this way was wedge exposed using white light, the following development processing steps A-E were performed.
I did it.

Treatment Step (38°C) The composition of the treatment liquid used in each treatment step is as follows.

Here, in treatment steps B and C, exemplified compound ■-34 was added to the treatment step, and in E, ■-34 was added to the bleach solution at 5X.
10-3 mol was added.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, sulfate 4.75 g Anhydrous sodium sulfite 4.259 Hydroquinylamine, l/2 sulfate 2.0 g Anhydrous potassium carbonate 37 .5g sodium bromide
139 Nitrilotriacetic acid trisodium salt (l hydrate) 2.5g Potassium hydroxide 1.09 Add water to make tQ.

[Bleach solution]

Ethyleneaminetetraacetic acid iron ammonium salt 100.09 ethylenenoaminetetraacetic acid 2 ammonium salt to, o9 ammonium bromide 150.0g glacial acetic acid
Add 10.0 mQ water to make IQ, and adjust to 1)) (= 6.0 using ammonia water.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make IQ, and adjust to 1) H=6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5m
& Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5m
12 Add water to make 112.

Table 1 shows the results of measuring the light density and residual silver amount of the wedge portion of the sample obtained after the development treatment, which corresponds to the same exposure amount.

In Table 1, samples 4 to 6 were developed in processing steps BE according to the method of the present invention.

As shown in Table 1, the method of the present invention can synergistically enhance the bleaching effect, reduce the amount of residual silver, and improve the light density even with changes in bleaching time (B vs. C, D vs. E). The good news is that it can be obtained extremely stably.

/ku1ゝ・1l-((＼、゛、111 Insert "extra" below [Example (2)] The bleaching accelerator shown in Table 2 was added to the first halide and soyon prevention layer of Sample 5 of Example (1). Samples 7 to 14, which were the same as sample 5 except for the addition, were prepared.

Next, exposure was carried out in the same manner as in Example (1), and processing steps F and G were carried out in the same manner as in development processing step A, except that the development processing step A and bleaching step were changed to 2 minutes 45 seconds and 3 minutes 45 seconds. After processing, the amount of residual silver and red density were measured.

As shown in Table 2, it can be seen that the effects of the present invention are exhibited even when a bleaching accelerator is used in color photographic materials, and that good desilvering properties and stable image density can be obtained.

that's all Hand°6 City IE’ book (direction; 05 April 15, 1986 6゜

Claims (1)

[Claims] A red-sensitive silver halide emulsion layer containing a coupler, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer are provided on a support, and drying of all the hydrophilic colloid layers on the side having the photosensitive layer. A multilayer silver halide color photographic light-sensitive material having a total film thickness of 18 μm or less is imagewise exposed, color developed, and then processed with a processing solution having bleaching ability in the presence of a bleaching accelerator. Color image forming method.