JPH03136034A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material hardly causing fog even after storage over a long period of time and having superior desilverability by incorporating a specified hardening agent into at least one of photographic constituent layers and a silver salt of a compd. having bleaching accelerating action into at least one of the photographic constituent layers. CONSTITUTION:At least one of a vinylsulfone hardening agent and an active hardening agent having a carboxyl group is incorporated into at least one of photographic constituent layers and at least one kind of silver salt of a compd. having bleaching accelerating action into at least one of the photographic constituent layers. A silver halide color photographic sensitive material hardly causing fog even after storage over a long period of time, having satisfactory desilverability and capable of shortening the time required for a desilvering stage can be obtd.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a silver halide color photographic light-sensitive material, which has particularly good desilvering properties, can be processed quickly, and is free from fog during storage of the light-sensitive material. This invention relates to a silver halide color photographic material that generates little generation.

[Prior art]

In general, the processing steps for silver halide color photographic materials (hereinafter also simply referred to as photographic materials) basically consist of two steps: color development and desilvering, and desilvering consists of a bleaching and fixing step or a bleach-fixing step. It has become.

In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps.

In recent years, there has been an increasing demand for faster processing of photographic light-sensitive materials. technology was desired. Conventionally, thiols, thiones, dithiones, etc. have been known as bleaching accelerators that are effective in speeding up the bleaching process, but even if these compounds are added to photographic materials as they are, they do not have sufficient desilvering properties. Not only is there little improvement, but there are many drawbacks such as decreased sensitivity and decreased color density, and it is difficult to say that it is an effective technique.

[Problems to be solved by the present invention]

In order to solve this problem, Japanese Patent Application No. 1-167747 and Japanese Patent Application No. 1-176832 propose that a silver salt as a bleaching accelerator be contained in a photographic light-sensitive material. According to these methods, desilvering properties are dramatically improved without causing a decrease in sensitivity or coloring density. It has been found that this method has the disadvantage that fogging is likely to occur.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material that exhibits less fog even during long-term storage, can shorten the time required for the desilvering process, and has good desilvering properties.

[Structure of the invention]

The above object of the present invention is to form a photographic structure by forming a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer on a support. In a silver halide color photographic light-sensitive material having layers, at least one of the photographic constituent layers contains:
Contains at least one vinyl sulfone hardener or carboxyl group-activated hardener, and at least one of the photographic constituent layers contains at least one silver salt of a compound having a bleaching accelerating effect. This was achieved using a silver halide color photographic light-sensitive material characterized by the following.

The present invention will be explained in more detail below.

A vinyl sulfone hardener is a compound having a vinyl group bonded to a sulfonyl group or a vinyl group-forming group, and preferably has at least two vinyl groups bonded to a sulfonyl group or a group capable of forming a vinyl group. It has one.

For example, a compound represented by the following general formula (V S -I) is preferably used in the present invention.

General formula (VS-I) L (Sow X)+ll In the above general formula (MS-1), L represents an m-valent linking group, represents a group that can be eliminated in the form of, for example, a halogen atom, a sulfonyloxy group, a sulfoxy group (including salts), a tertiary amine residue, etc.

m represents an integer from 2 to 10, and when m is 2 or more, -3O□
-X may be the same or different.

The m-valent linking group is, for example, an aliphatic hydrocarbon group (e.g.
Alkylene, alkylidene, alkylidine, etc., or
groups formed by combining these), aromatic hydrocarbon groups (
For example, arylene, etc., or a group formed by combining these) -0--NR'- (R' represents a hydrogen atom or preferably an alkyl group having 1-15 carbon atoms), -S , -N, -CO, So, So
It is an m-valent group formed by combining one or more bonds represented by w- or -SO,-, and -
When two or more NR's are included, those R's may be bonded to each other to form a ring. The linking group further includes those having a substituent such as a hydroxyl group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group, or an aryl group.

Specific examples of X include -CH, -CHl or CH2CH
iCI2 etc. are preferred.

Typical examples of vinyl sulfone hardeners are listed below. ■ CB, -CI (So, C)1. sO,cH-CH.

VS-2 CH2= CH30□(CH2)2SOzCH=CH2
S CH2CH2SO2(CH2),SO,C)ICH.

VS CH2= CH30*CH20CH2SOzCH-CH
2S-5 CH2=CH5(h(C)I2)zo(CHJ2S(h
CH-CH2S-6 CO3-CHSO2CH2CHC)12SO□C)I
= CH2H VS CH, -CH30□C)]2C)1cH2CHCH2S
o2CH-C)].

H cH 5-a Cl x = C)ISOgcHz C0N)ICHz
NHcOcHz So z CH= CHzS CHz -CHSO*CH2C0NH(CHz) zN
HcOcH2sO2cH-CHzS-16 C)+2 = CH5OzCHzCHC)lzso□C)
l=CH25o, Cl-CH.

VS 7 VS 8 CH, -C) ISO, CH2 CH25O, CH-CH.

5-19 VS 0 ((C)I* =CH5Oz)sccH*5Oz(CH
z)zscH2]ic.

M S -21 VS 0 CH2-CHSO□CHzCONH(CHz)xNHC
OCHzSOzCH=C)Ii5-tl VS-12 COCH2SO2CH TomiCH.

5-13 VS-14 CH2=CH3O2(C)li)zcONHCH2CH
2-CH5O2(CH2)2CONHCH25-15 cH3 CH.

VS-22 (C)! , = c) IsO, CH2), CS-23 VS -24 (CJ=CH5O2CHJxCCzHsS-28 SO□CH own CH2 VS -29 VS-30 C) I, = CHSO□(C[(z)iso□( C
HJzSQzCH=C[(tS-31 CHz -CH30I (CBrizO(CHt)2N
HON)I(C)lx)20(CHz)zsOtcH
= CH2S-32 CO(C1h)*SO□Cl = CH25-33 5-34 VS-35 (CHt -CB5(hNH)2cH*S-5- 36CH2=CHS(h(CI(z)zNH(CHz)
zNH(CHz)zsOzcH-C)1S-44CH2(CONHCH2So2CI-CH2).

VS-45 M S -46 C(Co(C1h)!5OICB-CI,)4S-47 V S -48 Nl(((CHt)zsOzcH=c)lx)zV S
-49 (H, c(co, oco, so□CH-CH2).

V S -50 C(CHtOCH*5OzCH=CHriaS-51 N((C)Iri!0CR2So, CH-CH,) 3S
-37 (CHz -CHSOz(CHt)*C0NCHz)
zcHzCHl VS-38 VS -39 VS-41 CaH17C(CH2SO2CH=CH2)zV S
-42 (CHz-CuSO4(Jlz)zCHCH(CHzS
OzC)I=C)Iz)zCHz=CH5O.

5OxCH-CHt VS-52 (CI(z-CHSO2CHzhCCHSOz(Cut
)zcI2S-53 CHt-CHSOzCH=CHi VS-54 CH2-CB5(hcToc(CHzSOz(CHri2
0sOsθNaΦ].

VS-55 C)1ssOs(CHt)2SO□(cow)*oso
□CH.

VS-56 VS-57 The vinyl sulfone hardener used in the present invention is described, for example, in German Patent No. 1.100.942 and US Pat. No. 3,490.
．． Aromatic compounds such as those described in Japanese Patent Publication Nos. 44-29622, 47-25373, 4
Alkyl compounds bonded with hetero atoms as described in Japanese Patent Publication No. 7-24259, sulfonamides and ester compounds as described in Japanese Patent Publication No. 47-8736, etc., and ester compounds described in Japanese Patent Publication No. 49-24435, etc. 1,3,5-tris[β-(vinylsulfonyl)propionyl]-hexahydro-s-triazine as shown in JP-B No. 50-35807, JP-A No. 51-44164, etc. Compounds and JP-A-59-
18944, etc., and which acts by activating carboxyl groups will now be explained in detail.

In the present invention, a hardening agent that acts by activating carboxyl groups (hereinafter referred to as a carboxyl group-activated hardening agent) refers to a hardening agent that reacts with carboxyl groups in the binder.

Examples of the hardening agent in the present invention include compounds represented by the following general formulas (H-1) to [H-■].

General formula CH-I) where R1 and R2 represent an alkyl group (e.g. methyl group, ethyl group, benzyl group, phenethyl group, 2-ethylhexyl group, etc.) or an aryl group (e.g. phenyl group, naphthyl group, etc.), It is also preferable that they be bonded to each other to form a heterocycle together with the nitrogen atom. Examples of the ring include a pyrrolidine ring, a piperazine ring, and a morpholine ring.

R3 is a substituent, for example -NR'R'(R' and R5 are R
1, synonymous with R1), a halogen atom, a carbamoyl group, a sulfo group, a ureido group, an alkoxy group, an alkyl group, etc. R3 includes those having a substituent, and examples of the substituent include a halogen atom, an alkyl group, a carbamoyl group, a sulfo group, a sulfooxy group, and a ureido group.

m represents O to 5, but when m≧2, the plurality of R3s may be the same or different from each other.

Xe represents an anion, and preferable examples include halide ion, sulfate ion, sulfonate ion, C(I
Q, Q, BF, e, PF, e Natoka Rarel.

a represents 0 or l, n represents 0 to 2, and n is 0 when forming an inner salt.

General formula (H-11) R'-N-C-N-R" where R1 and R2 are a cycloalkyl group (e.g. cyclohexyl group) or an alkyl group (e.g. methyl group, ethyl group, 2-ethylhexyl group, etc.) In addition, alkoxyalkyl groups such as methoxyethyl groups, aralkyl groups such as benzyl groups and phenethyl groups, 1! Here, R3 is an alkylene group (e.g. ethylene group, propylene group, trimethylene group, etc.), and R446 and R6 are alkyl groups ( For example, methyl group, ethyl group, etc.)
This includes cases in which two of R' to R6 combine to form a heterocycle (eg, pyrrolidine ring, piperazine ring, morpholine ring, etc.) together with a nitrogen atom, or cases in which they have a substituent.

Preferred examples of the substituent include carbamoylpho groups such as diethylcarbamoyl and piperidinocarbonyl.

m represents 0 or l, Xe represents an anion, halide ion, sulfonate ion, sulfate ion, CQO4e
, BF4e, PFae are preferred. Further, when forming an inner salt, m is 0.

In the formula, R'+2 alkyl group (for example, methyl group, ethyl group, butyl group, etc., as well as aralkyl group such as benzyl group, 7enethyl group) or aryl group (for example, phenyl group,
Naphthyl group, etc.). These groups further include those having a substituent, and examples of the substituent include a carbamoyl group, a sulfamoyl group, and a sulfo group. R2, R
3 is a hydrogen atom or a substituent, such as a halogen atom, an acylamido group, a nitro group, a carbamoyl group, a ureido group, an alkoxy group, an alkyl group, an alkenyl group, an aryl group,
It is also preferable that it represents an aralkyl group or the like, and that R2 and R3 combine to form a condensed ring together with the pyridinium ring skeleton.

X represents a group that can be eliminated when the compound represented by the general formula (H-III) reacts with a nucleophile. Preferred examples include a halogen atom, a sulfonyloxy group, and (S represents an alkyl group or an aryl group).

When X represents a sulfonyloxy group, it is also preferable that X and R1 are bonded.

Ye represents an anion, such as halide ion, sulfonate ion, sulfate ion, CQO+e, BF4ePF
, e etc. are preferred.

m represents 0 or l, and when forming an inner salt, m is 0
It is.

General formula (H-IV) In the formula, R141 is defined as 1 in general formula (H-1:l).
It is exactly the same as the definition of t4z, and R3 represents an alkyl group (for example, a methyl group, an ethyl group, a butyl group, or an aralkyl group such as a benzyl group or a phenethyl group) or an aryl group (for example, a phenyl group, a naphthyl group, etc.) .

xe is an anion, and includes a chloride ion, a sulfonate ion, a sulfate ion, and Cff0. e, BF, e
pp, 13, etc. are preferred.

General formula (H-V) General formula (H-Vl) R'-C=N-R" 1 In the formula, R', R" and R", R' (7) definition is the general formula (
R1 in H-I). It is exactly the same as the definition of R1,
Furthermore, R1 and R3 may form a ring.

xl represents a group that can be eliminated when reacting with a nucleophilic reagent, and is preferably a halogen atom, a sulfonyloxy group (preferably alkylsulfonyloxy or arylsulfonyloxy), an l-pyridium group, or an imidyloxy group (e.g. phthalimidyloxy). , succinimidyloxy, glutarimidyloxy), an azolyloxy group, and an ammonio group.

Y□. Examples of the anion represented by include norogen ion, sulfonate ion, sulfate ion, coo4e
, Bp, e, pp, e, phospho*-to ion, and phosphate ion.

In the formula, R14! is an alkyl group, alkenyl group, cycloalkyl group, aryl group, aromatic heterocyclic group or -NR3R
'(R'', R' represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or aromatic heterocyclic group, R3
44 is bonded to form a ring). Xl
is the same as the definition of Xl in general formula (HV).

General formula [H-■] In the formula, RIJ2 and R3, R4 and R5, R'c, R1 in the general formula f:H=I). It is the same as the definition of R1, and XI is x, g, y, e in the general formula (H-V)ilm.
is the same as the definition of Ylo in general formula [H-V].

General formula [H-■] H-1-2 In the formula, R1 represents an aryl group, 2 represents a group of nonmetallic atoms necessary to form an aromatic heterocycle, and the ring formed by R1 and Z is a substituted Including those with groups.

Ye represents an anion, m represents 0 or 1, and m is 0 when forming an inner salt.

As the carboxyl group-activated hardener used in the present invention, there are other preferable compounds in addition to the compounds represented by the general formulas (H-I) to [H-■].

Specific examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

-I -4 -1 ■ -I -1-7 -I-12 ■ -I-15 H-1[-2 H-I[-3 H-111-3 H-111-4 H-I[[- 5 H-111-6 Q -I-6 H-111-1 H-111-2 -V-1 -V-2 -V 3 -V-4 -5 -6- -V 2 l-2 ShiU n ShiU -V-7 -V-13 Shit -V-9 -V-IQ H-■-l ((CH3)2N) sP CQ H-■-2 C(C)Is)zN) sP C(1H -■-1 H-■-2 H-■-3 H-■-4 -0-9 -0-11 -0-12 -0-13 -0-14 -0-15 -0-17 Above compounds For example, JP-A No. 49-51945,
No. 51-59625, No. 61-9641, No. 62-
No. 262854, No. 62-264044, No. 57-4
No. 4140, Special Publication No. 57-46538, No. 58-50
No. 669, JP-A-51-126125, JP-A No. 52-48
No. 311, No. 62-68866, No. 62-68867
No. 61-128241, No. 62-234152, No. 52-54427, No. 60-225148, No. 61-240236, No. 50-38540, No. 52
-93470, 56-43353, 58-11
No. 3,929, US Pat. No. 3,321,313, etc., it can be easily synthesized by known techniques.

The vinyl sulfone hardener and the carboxyl group-activated hardener used in the present invention may be used alone, or
It may be used in combination in any proportion, and may also be used in combination with other hardening agents.

These vinyl sulfone hardeners and carboxyl group-activated hardeners are dissolved in water or organic solvents, and are combined with a binder (
For example, gelatin) is used in an amount of o,oos to 20% by weight, preferably 0.02 to 10% by weight.

For addition to the photographic layer, a batch method or an in-line addition method is adopted.

The layer to which these hardeners are added to the photographic layer is not particularly limited, and may be added to one uppermost layer, one lowermost layer, or all layers, for example.

The binder is preferably one having an amino group and a carboxyl group, as long as it causes a hardening reaction with the hardening agent used in the present invention, but it is usually advantageous to use gelatin.

Gelatin includes lime-processed gelatin, acidified gelatin, Bu
ll, Soc, Sci, Phot, Japan, No.
16.30 (1966), as well as gelatin derivatives (eg, acid halides, acid anhydrides, incyanates, bromoacetic acid,
The silver salts of compounds having a bleaching accelerating effect of the present invention obtained by reacting various compounds such as alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds include the following general Examples include compounds represented by formulas (I) to [XI[I].

General Formula (II[) In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocycle, and R1 represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or an amino group.

In the formula, R3 and R1 each represent a hydrogen atom, an alkyl group, a hydroxyl group, a carboxyl group, an amino group, an acyl group, an aryl group, or an alkenyl group. A is a formula in which Qo represents an atomic group necessary to form a sulfur-containing heterocycle, X is OlS or NR (R represents a hydrogenated or n1-valent heterocycle residue, and 0 or -NR". Here, R and R' have the same meaning as R2 and R1, respectively, X' has the same meaning as X, Z is an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, and in the formula, R8 and R9 is
Each represents a divalent metal atom group, R'' represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic residue, or an amino group, and n1 to n6 and m1 to m4 each represent a group of 1 to 6 atoms. An integer, m represents an integer of 0 to 6. B represents an alkylene group, R4 and R each represent R2
and R1. However, R4 and R may each represent -B-SZ, or R3 and R3, R and R
'R.

and R8 may be combined with each other to form a ring.

Represents the general formula (IV), where R3° is an alkyl group or -(CH2)n, so
, represents 0. (However, R1゜ is -(CH2)n, So,
The digit of e and α represent O, and when it is an alkyl group, it represents l.

)Ge represents an anion. n represents an integer from 1 to 6.

General Formula (V) In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocycle.

General formula CVI) In the formula, DI, DI, D, and B4 each represent a simple bond or a hydrocarbon chain, and Q l+ Q 2+ Q
s and q4 represent 0, 1 or 2, respectively.

General formula [■] In the formula, X2 is a hydrogen atom, R+s, C00M',
-OB.

503M', -CONHz, -5OtN)l*, -N
Hz, -CN, -CO2R+a.

-5OJ+s, -OR+s, -NR+@R+y,
-3Rth, -5O3R+s.

-NHCOR1m, -NH3O□R+a, -0COR
1s or -3JR+i, and Y! represents an alkyl group of 11.R1, represents -NR,. R2
□.

-0J2 or -5R12, R2° and Rz+ are
Each represents a hydrogen atom or an alkyl group, and R22 is R1
, represents the atomic group necessary to form a ring by combining with .

R2° or R21 may be combined with RIB to form a ring. M' represents a hydrogen atom or a cation.

General formula [■] is represented, and m and n each represent an integer of 1-10. R++i l! +R131R14, Rls+RIF
and Rha are each a hydrogen atom, an alkyl group, an acyl group, or in the formula, Ar represents an arylene group or a divalent organic group containing an arylene group, B2 and B3 each represent an alkylene group, and R! 31R24+R! S and R2° are
Each represents a hydroxy-substituted alkyl group, and X and y each represent 0 or l. G' represents an anion, 2
represents 0, 1 or 2.

General formula (ff) General formula (XI) In the formula, R27 and R28 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R2 represents a hydrogen atom or an alkyl group, and R3° is a hydrogen atom Or a carboxyl group.

General formula [X] In the formula, 2, . 22,2 and Z4 each represent a carbon atom or a nitrogen atom, and at least among these, in the formula,
R31 and R32 each represent a hydrogen atom or a substituent.

General Formula (XI) In the formula, R33+R34+R35 and R36 each represent a hydrogen atom or a substituent.

General formula [XI[I) R,, -3Ag In the formula, R17 represents an alkyl group, an aryl group, a heterocyclic group, an acyl group, a thioacyl group, a carbamoyl group, or a thiocarbamoyl group, and each group has a substituent. You may do so.

In general formula [I], the heterocycle formed by Q and the heterocycle represented by R1 each include a fused -\terocycle (for example, a fused 5- to 6-membered unsaturated ring),
The alkyl group represented by R1 preferably has 1 to 5 carbon atoms. Further, the heterocycle formed by Q and each group represented by R1 include those having a substituent (for example, an alkyl group, a carboxyl group, a sulfo group, an acyl group, etc.).

In general formula (If), the heterocycle formed by Qz includes a fused heterocycle (for example, a fused 5- to 6-membered unsaturated ring) and a substituent (for example, an alkyl group,
aryl group, carboxyalkyl group, alkoxycarbonylalkyl group, halogen atom, vinyl group, anilino group, acylamino group, sulfonamide group, etc.).

In general formula (1), the alkyl group represented by R,, R,, R/' and the alkylene group represented by B each preferably have 1 to 6 carbon atoms, and R,.

The acyl group represented by R1 preferably has 2 to 4 carbon atoms.

In addition, the heterocyclic group represented by A, R// includes a fused heterocycle (for example, one in which 5- to 6-membered unsaturated rings are fused), and each group represented by R2, R3, A, and R'' Groups include those having substituents (eg, hydroxyl groups, alkyl groups, etc.).

In general formula (TV), the groups represented by R, , R, include those having substituents.

In general formula [v], the heterocycle formed by Ql contains a fused heterocycle (e.g., a fused 5- to 6-membered unsaturated ring or saturated ring) and a substituent (e.g., carboxyl group, sulfonate ring). (groups, etc.).

In the general formula (Vl), the hydrocarbon chains represented by D8 to D may be saturated or unsaturated, such as alkylene,
Examples include alkenylene, and those having 1 to 8 carbon atoms are preferred. In addition, the sulfur-containing heterocycle is a fused heterocycle (for example, 5-
6-membered saturated ring, fused unsaturated ring), and substituents (e.g., hydroxyalkyl group, hydroxyl group,
carboxyalkyl group, etc.).

In the general formula [■], Rrl=Rla+Rx. .

The alkyl group represented by R21 preferably has 1 to 1 carbon atoms.
6.

In the general formula [■], the arylene group represented by Ar includes a phenylene group, a biphenylylene group, etc.
The divalent organic group containing an arylene group includes a combination of an arylene group and an alkylene group and/or a hetero atom (for example, an oxygen atom).

B,, an alkylene group represented by B, and R13 to R2,
The hydroxy-substituted alkyl group represented by is preferably one having 1 to 6 carbon atoms.

In general formula [X], 2. ．． 22,2. When z4 is a carbon atom, it includes those having a substituent (for example, an alkylthio group, an aryl group, a carboxyalkyl group, an amino group, a carboxyalkylthio group, an arylthio group, a heterocyclic group, an aryloxy group, an acyloxy group).

In general formula (n), R31 or R3! Examples of the substituent represented by include an alkyl group, an alkoxy group, an aryl group, a carboxyl group, a halogen atom, an amino group, a hydroxyl group, and a sulfo group.

In general formula (III), examples of the substituent represented by R33 to R36 include an alkyl group, an alkoxy group, an amino group, a hydroxyl group, a mercapto group, an acylamino group, and a carbamoyl group.

In general formula (Xlll), when R37 has a substituent, examples of the nuclear substituent include an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a carboxyl group, an amino group, an ammonium group, an alkoxy group, a sulfonyl group, and a sulfonyl group. group, acyl group, thioacyl group, carbamoyl group, thiocarbamoyl group, -5Rss group (Rxa represents a hydrogen atom or a silver atom).

The compounds of the present invention represented by the general formulas (I) to (xm) can be represented as (BA).Ag.

Typical specific examples of the compound (BA) and the compound represented by the general formula (XI[[) are listed below, but the invention is not limited thereto.

Exemplified compound (I-1) (1-2) (I −
9) (I-10) (I-
3) (1-4) (I -11) II3 (1-5) (1-6) CHzGHzCOOH (I[-1) (II -2) II3 Cm -3) (IF-4) (1- 7) (I-8) (u -5) (n-6) (II -7) (■ 8) (n-9) (II -10) (■ -11) (■ ~12) (■ 13) (■-14) (n -15) (n -16) (■ 3) (I[[-4) (I[l -5) S'l II CH+-NH-C-NHNHC H CHl (III-6 ) H2N-C3NHNHCS NH.

(Iff-7) HzN-CSNH (CI(z)zNHcsNH.

(I[+-8) (III 9) (■ 17) (■ 19) (■ 21) (n -23) (■ l) (I[l　-10) (III-11) (■ 12) (I[[-13) (I[[-14) (II-18) (II = 20) (n -22) ([-2) (III-17) S (III-18) (I[+-19) (Iff-20) (I[I-21) ζ (III-22) (III-23) (I[I-24) (V- 1) (V-2) (V-3) (Vl- 1) (Vl-2) (Vl-3) (Vl-4) (Vl-5) (Vl-6) (III-25) (m-26) (I[I-27) (IV-1) CH.

CH3 (IV-3) C) I$ (Vl-7) (Vl-8) (Vl　-9) (Vl　-10) (Vl　-11) (VT-12) 1 (Vl　-13) (Vl-14) (Vl-15) (Vl　-16) (Vl-17) (~1-1) (■-2) (■-3) (■-4) (■ 5) (■-6) (■− ) (■-2) (■ 3) (■-4) (■-5) (■-6) C)lzNH(CH2C)IzOH)z(■-7) (■ 8) (■ 9) (■ 10) (■ 11) (■-7) (I!- l) (■-3) (rX-5) CH.

″(■-12) (II-2) (4-4) (X-1) (X-2) (X-3) (X-4) (X-5) (X-6) (II-1) (n-2) (n-3) (n-4) xm - Nl2-CH2CH2-5Ag XI[l-2 XI[I　　-3 XI[[-4 HOOC-CHxCHz-SAg XI[I- xm-a Xnl -7 XI[l-8 XI[[-9 XIII -10 (n-5) (n-6) (II[- 1) (III-2) (III-3) (n-4) (III-5) (nr-6) C8゜ (n[-7) (III-8) XI[I　-11 XI[I　　-12 XII[-13 Xnl-14 C, Fl, C00H XIII-15 Xl11-16 Xllll-17 XI[[-18 Xllll-19 XIII-20 X■ 21 m-22 XI[l-23 χm 4 m-25 X[[l-26 XI [I 6 m-37 x■ 9 XI[l-40 XIII-41 0OC CH, CH, SCH, CH, SAg m-42 0OC CH2CHzOCH,CH,SA,g XII[-43 m-27 XIII-28 XIII-29 XI[[-30 XI [l-31 m-32 X■ 3 XI[+-34 XI[[-35 m-44 x■ 5 m-47 1 CH b) C) ltcHzcsAg l-49 Xllll-50 X1ll-51 DI-52 The above compound (BA) is described, for example, in British Patent I.

No. 138,842, JP-A-52-20832, JP-A No. 53
-28426, 53-95630, 53-10
No. 4232, No. 53-141632, No. 55-171
No. 23, No. 60-95540, No. 61-75352, No. 61-83537, U.S. Patent No. 3,232.936
No. 3,772.020, No. 3,779,757, No. 3,893.858, and the like.

The silver salt of the present invention can be easily synthesized by mixing an aqueous solution of the above compound and an aqueous solution of silver nitrate.

The silver salt of the present invention only needs to be present in the color photographic light-sensitive material, and may be present in either the photosensitive layer or the non-photosensitive layer, but is preferably present in the non-photosensitive layer, particularly in the photosensitive layer closest to the support. Preference is given to a non-photosensitive layer present between the layer and the support.

The amount added is based on the photosensitive material IIo! per I x 10-'
~100 g is preferred, and I x 10-'' ~ Ig is particularly preferred.

Next, a typical synthesis example of the silver salt of the present invention will be described. Incidentally, since it is preferable to add the compound to the photosensitive material in the form of a dispersion, the method for preparing the dispersion is also described.

Synthesis of silver salt of compound 1-2 19.1 g of rhodanine-3-acetic acid (I-2) was
Dissolved in 0 mQ of water, 169 g of 1O% silver nitrate aqueous solution was added to 1
Added in 5 minutes. After further stirring for 2 hours, the white crystals formed were crushed, washed with 2000+1172 water, and dried under vacuum to obtain 24.1 g of the target compound.

Preparation of dispersion 14.9 g of the compound synthesized above (silver salt of ■-2)
, 5% Alkanol XC (manufactured by DuPont) 10m7+
and 300 ml of water were added and dispersed for 12 hours using a ball mill to obtain a dispersion.

Synthesis of silver salt of compound Xl-2 31 g of 4-sulfobenzotriazole (n-2) was mixed with 1
Dissolved in 00100O water, 1O% silver nitrate aqueous solution 338
g was added over 30 minutes. After further stirring for 2 hours, the white crystals formed were collected by filtration, washed with 2000 mQ of water, and dried under vacuum to obtain 46.3 g of the target product (silver 4-sulfobenzotriazole).

Preparation of dispersion 20 g of 4-sulfobenzotriazole silver, 5% alkanol XC (manufactured by DuPont) 10 + n12 and water 40 g
0ml was added and dispersed in a ball mill for 12 hours to obtain a milky white dispersion.

The silver 10-genide emulsion used in the present invention is a conventional silver 10-genide emulsion such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used can be used.

Silver halide grains used in silver halide emulsions are
The grains may have a uniform silver oxide composition distribution within the grain, or may be core/shell grains in which the silver oxide 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.

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) may be used alone or in combination.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

Furthermore, by force/twisting with colored couplers, competing couplers, and oxidized forms of developing agents, which have the effect of color correction, development accelerators, bleaching accelerators, developing agents, silver halide solvents, toning agents, and hardening agents are produced. Compounds that release photographically useful fragments can be used, such as capri agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

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

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazoloazole couplers, pyrazolopenzimidazole couplers, open chain acylacetonitrile couplers, indazole couplers, etc. can be used.

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

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

For photosensitive materials, formalin scavenger-fluorescent brightener,
A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retarder, and a bleach accelerator can be added.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

Typical specific examples of processing steps used to process the photographic material of the present invention are shown below.

(1) Color development - bleach fixing → water washing (2) color development → bleach fixing → small amount of water washing → water washing (3) color development - bleach fixing - first stabilization (4) color development - bleach fixing - stable (5) color development - Bleach-fixing - 1st stability - 2nd stability (6)
Color development → washing with water - bleach-fixing → washing with water (7) Color development → bleach acceleration - bleach-fixing → stabilization (8) Color development - bleach acceleration - bleach-fixing - washing (9) color development - pre-fixing - bleach-fixing - stabilization (
10) Color development → Pre-fixing → Bleaching → Stable (11) Color development - Bleach - Washing → Fixing - Washing → Stable (12) Color development - Bleach-fixing - 1st stable (13) Color development - Bleaching → Fixing → 1st
Stability → 2nd stabilization (14) Color development → Bleaching → Washing with a small amount of water → Fixing → Washing with a small amount of water -
Washing with water - Stable (15) Color development → Bleaching → Bleach-fixing - 1st stability → 2nd stability (16) Color development - Bleaching acceleration - Bleaching constant → 1st stability →
Second Stability (17) Color Development - Small amount of water washing - Bleaching → Small amount of water washing → Fixing →
Small amount of water washing - Water washing - Stable (18) Color development - Bleaching acceleration - Bleach One small amount of water washing Constant coloring One small amount of water washing One water wash → Stable (19) Black and white development - Water washing (or stable) → Reversal → Color development → Bleach Constant coloring - Water washing (or omitted) (20) Black and white development - Water washing (or stable) - Reversal - Color development → Bleaching acceleration → Bleach constant - Water washing (or omitted) - Stable (21) Black and white development - Water washing (or stable) - Reversal - Color development Development → bleach fixing - washing with water (or omitted) - stable (22) black and white development - washing with water (or stable) - reversal → color development - accelerated bleaching - constant bleach fixing - washing with water (or omitted) - stable Furthermore, bleaching in the above steps An accelerator is a pre-bath containing a bleach accelerator.

Any bleaching agent can be used as a bleaching agent in the bleaching solution or bleach-fixing solution for processing the photographic material of the present invention, such as red blood salt, iron chloride (British Patent No. 736.881).
No. 56-44424), persulfuric acid (described in German Patent No. 2.141.199, etc.), hydrogen peroxide (described in German Patent No. 2.141.199, etc.),
(described in Japanese Patent Publication No. 58-11617, No. 58-11618, etc.), as well as aminopolycarboxylic acid ferric complex salts such as ethylenediaminetetraacetic acid ferric complex salts, and particularly preferred specific examples include the following: It is a ferric complex salt of the aminopolycarboxylic acid shown below.

[11 Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine/N-(β-hydroxyethyl)-N,N',N'-triacetic acid [411,3-Diaminopropanetetraacetic acid [51 Triethylenetetraminehexaacetic acid] Acetic acid [61 cyclohexanediaminetetraacetic acid [7] 1.2-diaminopropane tetraacetic acid [8]] 1.3
-Diaminopropane-2ol-2-tetraacetic acid [9] Ethyl ether diamine [1O] Glycol ether diamine tetraacetic acid [111 Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [ 14
] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16]
] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine N-(β-hydroxyethyl)-N,N',N'-triacetic acid sodium salt [18]
Propylenediaminetetraacetic acid sodium salt [19] Ethylenediaminetetramethylenephosphonic acid [20] Cyclohexanediaminetetraacetic acid sodium salt [211 Diethylenetriaminepentamethylenephosphonic acid [22] Cyclohexanediaminetetramethylenephosphonic acid [23] Nitrilotriacetic acid [24] Iminoniacetic acid [25] Hydroxyethyliminodiacetic acid [261 Nitrilotripropionic acid] [27] Nitrilotrimethylenephosphonic acid [28] Iminodimethylenephosphonic acid [29] Hydroxyethyliminodimethylenephosphonic acid [30] Nitrilotriacetic acid monosodium salt These organic acids Among the ferric acid complex salts, the effects of the present invention are effectively exhibited for compounds with large molecular weights, and preferably the molecular weight of the organic acid is 300 or more.

Among these organic acids, a compound that exhibits the effects of the present invention is more preferably diethylenetriaminepentaacetic acid.
, 1,3-diaminopropanetetraacetic acid, 1+2-diaminopropanetetraacetic acid, 1,4-diaminobutanetetraacetic acid, glycol etherdiaminetetraacetic acid, and cyclohexanediaminetetraacetic acid, particularly preferably '' is diethylenetriaminepentaacetic acid, 1. 3-diaminopropanetetraacetic acid is mentioned.

Ferric complex salts of aminopolycarboxylic acids can be used as free acids (hydrogen salts), alkali metal salts such as sodium salts, potassium salts, lithium salts, ammonium salts, or water-soluble amine salts, such as triethanolamine salts. Preferably potassium, sodium and ammonium salts are used. At least one type of these ferric complex salts may be used, but two or more types can also be used in combination.

The amount used can be arbitrarily selected and must be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but it is generally used at a lower concentration than other aminopolycarboxylate salts because of its high oxidizing power. can. For example, it can be used in an amount of 0.01 mol or more per tQ of working liquid, preferably 0.05 mol or more.
~0.8 mol is used.

In addition, the solubility of the replenisher is -
It is preferable to use it concentrated in a cup.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of sample) The following l was prepared on a subbed cellulose acetate support.
Multilayer color photosensitive material sample N of multilayer #I composition consisting of jl composition
o. l-NO. 34 was created.

The coating weight is the amount expressed in g/m2 in terms of silver for silver halides and colloidal silver, and the amount expressed in g/m2 for additives and gelatin.
Sensitizing dyes, couplers and DIR compounds are expressed in moles per mole of silver halide in the same layer. The silver salts of the present invention (tc shown in Table 1) were each added at 3 mmol/m2 to the first layer (IC) in the form of a dispersion or an aqueous solution.

The emulsion contained in each color-sensitive emulsion layer was optimally sensitized using sodium thiosulfate and chloroauric acid.

C4) 1゜ -2 H -3 H y-1 CM-1 Sensitizing dye I Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ (CHtJsSO,- (CHz)ssOsH’N(CzHs)s-1 H -2 H -3 H Sensitizing dye V Comparative hardener H S H Hereinafter, each layer with the above composition is described above) Ic, IL-1.

R-1, R-2, IL-2, G-1, G-2, YC.

Indicated by the abbreviations B-1, B-2, Pro-1, and Pro-2. In addition to the above-mentioned components, a surfactant was added to each layer as a coating aid.

Thereafter, wedge exposure was performed according to a conventional method, and the following development treatment was performed.

Processing process (38℃) Color development 3 minutes 15 seconds bleaching
White Fixed as listed in Table 1
Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is shown below.

Color developer 4-Amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/21jii acid salt 2.0g Anhydrous potassium carbonate 37.5g potassium iodide
1.9mg potassium bromide
1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2.5g potassium hydroxide
Add 1.0g water to make 1Q. (pH-1
0,02) Bleach solution (formulation A) Iron ethylenediaminetetraacetic acid (I) Ammonium salt 100.0g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10.0g water and N
2 and adjust to p) 16.0 using aqueous ammonia.

Bleach solution (formulation B) 1.3-diaminopropanetetraacetic acid iron(II[) ammonium salt 180.0g 1.3-diaminopropanetetraacetic acid diammonium salt 4.0g ammonium bromide 128.0g ammonium nitrate 118.0g glacial acetic acid
69.0g ammonium water (2
5%) Add 30n12 water to make IQ, and use ammonia water to adjust to pi (4,5).

Fixer Ammonium thiosulfate 175.0g Anhydrous ammonium sulfite 8.68 Sodium metasulfite 2.3g Add water to make 112, and adjust to pH 6.0 using acetic acid.

Stabilizing liquid formalin (37% aqueous solution) 1.5m
αConidax (manufactured by Konica Corporation) 7.5+
Add oα water to make 112.

Next, the same samples 1 to 34 were subjected to wedge exposure according to a conventional method, and the following development treatment was performed.

Processing steps (38°C) Color development 3 minutes 15 seconds Bleach-fixing Table 1 Water Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the processing solution used in each processing step is shown below.

Color developer: Same bleach-fix solution as above Ethylenediaminetetraacetic acid iron (II) Ammonium 60.0g Ethylenediaminetetraacetic acid ammonium salt 3.0g Ammonium thiosulfate (70% solution) 130.0m + 12 Ammonium sulfite (40% solution) 27. 5+
sff color developer ioo,
o■Q Add water to bring the total volume to tQ, and adjust the pH to 7.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution: Sample 1, which was the same as above, was subjected to wedge exposure, then color development without bleaching, followed by constant color development, washing with water, stabilization, and drying.

The amount of residual silver in the maximum density portion of this sample was measured using fluorescent X-rays, and with this as the remaining silver amount 100%, the relative silver residual rate in the maximum density portion of each sample was determined.

Next, each sample was divided into two parts, one part was stored at 50°C and 80% relative humidity for 7 days, the other part was stored in a refrigerator (5°C) for 7 days, and then the conventional method was used. Wedge exposure was performed and development processing was performed using the following processing steps.

Processing steps (38°C) Color development bleaching Water washing Fixing in water Washing Stabilization Drying In each of the processing steps, the processing solution used was the same as above (however, the bleaching solution used was Formulation A).

The optical density of the minimum density part of the obtained sample was measured using an optical densitometer PDA-65 manufactured by Konica Corp., and the optical density was determined as blue, green, red,
Calculate the fog density change of each photosensitive layer ΔFog - blue, ΔF
og-green and ΔFog-red.

3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 1 minute 30 seconds From the above results, sample No. 3 containing the silver salt of the present invention and a comparative hardener was desilvered. Sample No. 1 has excellent properties, but has a large increase in fog during storage, and does not contain the silver salt of the present invention.
Samples Nos. 1 and 2 have poor desalination properties, but samples Nos. 094 to 34 containing the silver salt of the present invention and the hardening agent of the present invention have a small increase in fog and are used as bleaching solutions (A).

(B), it can be seen that the desalting properties are excellent no matter which bleach-fix solution is used.

Example 2 I-6, I as a compound (BA) for making the silver salt of the present invention
-9,l-10,n-1,1[-23,nl-13,l
ll-24, IV-1, V-2, Vl-6, Vl-1゜■-2. ll-5. For X-3, n-4 and lN-5 (BA) ・Also as Ag, l-4, ff-1
1゜DI-15, DI-33, ll-42, ff-43
, ■-44.111-45, and ff-47 were conducted in exactly the same manner as in Example 1, and the effects of the present invention were confirmed.

Example 3 VS-28, VS-29, VS-32, VS-33, V
S-38, VS40, VS-53, VS-54, VS-
55, VS-56, H-I-2, H-11-3, H
-III -5, H-V-1, H-Vl-2, H-0-
Samples were prepared in exactly the same manner as in Example 1 using 5, H-0-9, and H-0-13, and experiments were conducted in exactly the same manner as in Example 1, and the effect of the present invention was confirmed. .

〔Effect of the invention〕

As described above, according to the present invention, it is possible to provide a silver halide color photographic light-sensitive material with excellent desilvering properties that causes less fogging even during long-term storage and can shorten the time required for the desilvering process. .

Claims (1)

[Claims] A silver halide color having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and at least one non-light-sensitive hydrophilic colloid layer as photographic constituent layers on a support. In the photographic light-sensitive material, at least one of a vinyl sulfone hardener or a carboxyl group-activated hardener is contained in at least one of the photographic constituent layers.
containing seeds and in at least one of the photographic constituent layers,
A silver halide color photographic material containing at least one silver salt of a compound having a bleaching accelerating effect.