JPH03144634A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve desilverability and to enable rapid processing by incorporating a specified compound in at least one of a photosensitive silver halide emulsion layers and the silver salt of a compound having a bleach promoting action in at least one of photographic constituent layers. CONSTITUTION:At least one of the photosensitive silver halide emulsion layers of the silver halide photographic sensitive material contains the compound capable of reacting with the oxidation product of a color developing agent and releasing a compound capable of scavenging said product or its precursor, typified by formulae I and II and the like, and at least one of the photographic constituent layers contains the silver salt of the compound having the bleach promoting action, thus permitting desilverability to the improved and rapid processing to be carried out.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, which has particularly good desilvering properties, can be processed quickly, has high sensitivity, and has excellent graininess. This invention relates to a silver halide color photographic material.

[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.

Recently, there has been an increasing demand for faster processing of photographic light-sensitive materials. Improved 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]

Regarding the above problem, as a result of intensive research, the present inventors have found that by incorporating a silver salt of a specific organic compound into a photographic light-sensitive material, the desilvering property is dramatically improved, as shown in Japanese Patent Application No. 1-176832. However, further detailed study revealed that photographic materials containing the silver salt have a drawback of poor graininess.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material that has good desilvering properties, can be processed rapidly, has high sensitivity, and has excellent graininess.

[Structure of the invention]

The above object of the present invention is to form 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 using a photographic TIII method. In a silver halide color photographic material having a blank layer, at least one of the light-sensitive silver halide emulsion layers contains a compound or a precursor thereof capable of reacting with an oxidation product of a color developing agent and scavenging the oxide. This has been achieved by a silver halide color photographic light-sensitive material which contains a compound capable of being released and which is characterized in that at least one layer of the photographic composition contains a silver salt of a compound having a bleaching accelerating effect.

The present invention will be explained in more detail below.

A compound capable of reacting with the oxidation product of the color developing agent in the present invention and scavenging the oxide, or a compound capable of releasing its precursor (hereinafter referred to as "rDSR compound").
is preferably represented by the general formula (DSR-I).

General formula (DSR-I) Coup-(Time)Q-Sc In the above-formation (DSR-I), Coup is a coupler residue capable of releasing (7ame→-5c) by reaction with an oxidized color developing agent. , and Tinge is Time
- Sc represents a timing group that can release Sc after it is released from Coup. represents a scavenger of an oxidized color developing agent or a precursor thereof, which can be scavenged by oxidized color developing agent, and a represents 0 or 1.

Furthermore, to specifically explain the compound represented by the general formula (DSR-13), the coupler residue represented by Coup is generally a yellow coupler residue, a magenta coupler residue, a cyan coupler residue, or a substantially It is a coupler residue that does not form an image-forming coloring dye, preferably the following - formation (DS
These are coupler residues represented by R-1a) to CDSR-1h).

General formula (DSR-I a) - Formation CD5
R-I b) 3 General formula (DSR-1c) General formula CD5R-I d) General formula CD5R-I e) General formula CD5R-I f) General formula (:DSR-I g) -Formation CD
5R-I h) In the above-formation (DSR-18) R
1 represents an alkyl group, an aryl group, or an arylamino group, and R1 represents an aryl group or an alkyl group.

In the above-formation CD5R-I b), R1 represents an alkyl group or an aryl group, and R4 represents an alkyl group, an acylamino group, an arylamino group, an arylureido group, or an alkylureido group.

In the above-formation CD5R-I c), R has the same meaning as R in -formation (DSR-I b), and R6 represents an acylamino group, a sulfonamide group, an alkyl group, an alkoxy group, or a halogen atom.

In the above-formation CD5R-I d) and (DSR-re), %R7 represents an alkyl group, an aryl group, an acylamino group, an arylamino group, an alkoxy group, an arylureido group, an alkylureido group, and Rfi represents an alkyl group, an aryl represents a group.

In the above-mentioned -formation (DSR-If), R9 represents an acylamino group, carbamoyl group, or arylureido group, and R8 represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or a sulfonamide group.

In the above-formation CDSR-Ig), R9 is of the general formula C
D5R-ID has the same meaning as D, and R1° represents an amino group, an acid amide group, a sulfonamide group, or a hydroxyl group.

In the above-mentioned - formation (DSR-1h), Ro represents a nitro group, an acylamino group, a succinimide group, a sulfonamide group, an alkoxy group, an alkyl group, a halogen atom, or a cyano group.

Also, during the above-mentioned formation, a in (DSR-Ic) is 0 to 3, n in CD5R-I f) and (osR-I h) is O to 2, and m in (DSR-rg)
represents an integer from O to 1, and when a%n is 2 or more, each R8 and R1 may be the same or different.

Each of the above groups includes those having a substituent, and preferred substituents include a halogen atom, a nitro group, a cyano group, a sulfonamide group, a hydroxyl group, a carboxyl group, an alkyl group, an alkoxy group, a carbonyloxy group, and an acylamino group. , aryl groups, etc., as well as so-called bis-type couplers.
Examples include those containing a coupler portion constituting a polymer coupler.

The lipophilicity exhibited by R1 to Ro in each of the above-mentioned formations can be arbitrarily selected depending on the purpose.

In the case of conventional image-forming couplers, the total number of carbon atoms in R1 to Ro is preferably from IO to 60, more preferably from 15 to 30. In addition, in the case where the raw dye is to be appropriately moved in the light-sensitive material by color development, the R.

The total number of carbon atoms from R1° to R1° is preferably 15 or less.

Couplers that do not substantially affect image-forming coloring dyes include those that do not form coloring dyes, as well as so-called run-off dye-forming couplers, in which the coloring dyes flow out from the light-sensitive material into the processing solution, and those that react with components in the processing solution. This refers to so-called bleaching dye-forming couplers that do not leave a color image after development, and in the case of run-off dye-forming couplers,
The total number of carbon atoms in R1 to R1° is preferably 15 or less, and furthermore, as a substituent for R1 to Rra, at least one carboxyl group, arylsulfonamide group,
Preferably, it has an alkylsulfonamide group.

In the above -forming CD5R-I), the timing group represented by Time is preferably the following -forming CD5R-
1i), designated as CD5R-IO or CD5R-1k:l.

In the formula, B represents an atomic group necessary to complete a benzene ring or a 7talene ring, and Y is bonded to the active point of the Coup (coupling component) of 10-■]. R1□, R1 and Ro represent a hydrogen atom, an alkyl group or an aryl group.

is substituted at the rose position, and the other is the -formation (DS
It is bonded to the SC of R-1).

-Formation [:DSR-r j] In the formula, Y, R+z, R,, respectively represent the above-mentioned -Formation CDSR-
Ii), RI5 represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, or a heterocyclic residue, and R4 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue. group, alkoxy group, amino group, acid amide group, sulfonamide group, carboxyl group, alkoxycarbonyl group, carbamoyl group, or cyano group.

In addition, the timing group represented by the above-mentioned -formation CD5R-Ij] is similar to the above-mentioned -formation CD5R-Ii), in which Y is in the molecule next to the Coup (coupling component) of the -formation (DSR-I). Time to release SC by nucleophilic substitution reaction
Examples of the group include those represented by the following -formation CD5R-I k).

General formula CD5R-I k) -Nu-D-E- In the formula, Nu represents a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, and the -formation CD5R-I)
It binds to the active site of the Coup (coupling component). E represents an electrophilic group having an electron-poor carbonyl group, thiocarbonyl group, phosphinyl group, or thiophosphinyl group.

This electrophilic group E is bonded to the heteroatom of Sc, and D
has a steric relationship between Nu and E, and after Nu is released from the Coup (coupling component), the intramolecular nucleophilic substitution is broken by a reaction that involves the formation of a 3- to 7-membered ring. and represents a binding group by which Sc can be released.

Further, the scavenger of the oxidized color developing agent represented by Sc (if Sc is a precursor, the scavenger generated from the precursor) is of the redox type and the coupling type.

- formation (DSR-I), when Sc scavenges the oxidized color developing agent by redox reaction, the Sc is a group capable of reducing the oxidized color developing agent, for example, Angew, Chew, Int. .

Ed, 17875-886 (1978), Th
e Theory of thePhotograph
ic Process 4th edition (Macmillan 1
977) Chapter 11, reducing agents described in JP-A No. 59-5247 and the like are preferred, and Sc may be a precursor capable of releasing such reducing agents during development. Specifically, it represents a cycloalkyl, alkenyl, or aryl group.

An aryl group or a heterocyclic group having at least two groups is preferable, an aryl group is especially preferable, and a 7-enyl group is more preferable. The lipophilicity of Sc is determined by the above-formed CD5R-Ia
) or like the coupler represented by DSR-1hl, any J2 may be linked depending on the purpose, but in order to maximize the effect of the present invention, the total number of carbon atoms in Sc is 6 to 50.
, preferably 6-30, more preferably 6-20.

When the Sc scavenges the oxidized color developing agent through a coupling reaction, the Sc can be a variety of coupler residues, but is preferably a coupler residue that does not substantially produce an image-forming color dye. The above-mentioned run-off dye-forming couplers, bleaching dye-forming couplers, and Weiss couplers that have a non-leaving substituent at the reaction active site and do not form dyes can be used.

-Formation (DSR-I) Specific compounds represented by Co゛up←Timeisc include, for example, British Patent No. 1546837, Japanese Patent Application Publication No. 150631/1983, Japanese Patent Application Publication No. 57-111536,
No. 57-11537, No. 57-138636, No. 6
No. 0-185950, No. 60-203943, No. 60
-213944, 60-214358, 61-
No. 53643, No. 61-84646, No. 61-867
No. 51, No. 61-102646, No. 61-10264
No. 7, No. 61-107245, No. 61-113060
No. 61-231553, No. 61-233741, No. 61-236550, No. 61-236551,
No. 61-238057, No. 61-240240, No. 61-249052, No. 62-81638, No. 62
There are those described in No. -205346, No. 62-287249, etc.

As Sc, a redox type scavenger can be preferably used, and in this case, the color developing agent can be reused by reducing the oxidized product of the color developing agent.

Next, DSR compounds represented by the above-formed CD5R-I) will be exemplified, but the present invention is limited to the following exemplified compounds. H D S R-14 D S R-15 -16 17 18 -19 5R-20 H S 22 NHSO*N(CHs)t S 23 -25 S -26 -27 DSR-28 DSR-29 5R-30 H - 31 -32 0 H3 S 33 Cθ S 34 0 S -35 1', Ill = 36 -37 38 "θ 5R-39 5R-40 5R-41 SR 2 H The DSR compound of the present invention is a photosensitive silver halide emulsion. Although it can be added to the photosensitive silver halide emulsion layer and/or the non-photosensitive photographic constituent layer, it is preferably added to the photosensitive silver halide emulsion layer.

Two or more types of DSR compounds of the present invention can be contained in the same layer. Also, the same DSR compound may be included in two or more different layers.

It is generally preferable to use these DSR compounds in an amount of 2 X 10-' to 5 XlO-' moles per mole of silver in the emulsion layer, more preferably lX10-3 to I X 10-'
'It's a mole.

In order to incorporate these DSR compounds into the silver halide emulsion according to the present invention or other photographic constituent layer coating solutions, if the DSR compounds are alkali-soluble, they may be added as an alkaline solution. If it is oil-soluble, for example, US Pat. No. 2,322,027, US Pat.
, No. 170, No. 2,801,171, No. 2,272.
According to the method described in No. 191 and No. 2,304.940, the DSR compound is dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, dispersed in the form of fine particles, and added to the silver halide emulsion. It is preferable to do so.

The above DSR compound is disclosed in Japanese Patent Application Laid-Open No. 57-138638,
No. 57-155537, No. 57-171334, No. 58-111941, No. 61-53643, No. 61
-84646, 61-86751, 61-10
No. 2646, No. 61-102647, No. 61-107
It can be synthesized by the method described in No. 245, No. 61-113060, etc.

The compound or its precursor that undergoes a coupling reaction or redox reaction with the oxidized developing agent, which is released from the DSR compound of the present invention during development in accordance with the image density, is released in accordance with the image density within the photosensitive emulsion layer. Correspondingly, it suppresses the pigment-forming reaction (coupling reaction), resulting in so-called intra-image effects such as sharpness of the image, and on the other hand, in other layers where it has diffused, it suppresses the pigment-forming reaction in that layer. It is possible to obtain two types of image effects, one producing a so-called inter-image effect, such as a masking effect that corresponds to the density of the image of the layer of the diffusion source and inhibits it.

The silver salt of the compound having a bleaching accelerating effect according to the present invention includes:
Compounds represented by the following -formation CI) to (XI[[) are exemplified.

In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocycle, and RI represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or an amino group.

In the formula, Qo represents an atomic group necessary to form a sulfur-containing heterocycle; It represents a carboxyl group, an amino group, an acyl group, an aryl group or an alkenyl group. A represents X' or n, a valent heterocyclic residue, and X represents -S, =O or -NR". Here, R and R' have the same meaning as R3 and R1, respectively, X' has the same meaning as -5-B-Y\,.

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 n, "n, and ml to m are each 1 to m5 represents an integer of 0 to 6. B represents an alkylene group, R1 and R each represent R1
and R1. However, R4 and R6 may each represent -B-5Z, or R2 and R1, R and R
'R.

and R6 may be combined with each other to form a ring.

-Formation [■] In the formula, R6 and R, each represent an R+o11i alkyl group or -(CH2)n1
Represents S03G. (However, RIO is -(CHz)n@5
O3e(7) (!l: pk, Q represents 0, and when it is an alkyl group, represents l.) Go represents an anion. ns represents an integer from 1 to 6.

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

General formula (Vl) In the formula, D, , D, , D, and D each represent a simple bond or a hydrocarbon chain, and Q t+q! IQ s and q represent 0.1 or 2, respectively.

-Formation [■] In the formula, X2 is a hydrogen atom, R, , -COOM', -
Oh.

-505M', -CONHz, -SO*NL
, -NHZ, -CN, -COJ+s.

-5OzRts, -0Rri, -NRrJrv, -5R
ra, -5OsRrs.

-N) IcORr 1-NH5O2Rl @ , -0
CORl l or -So! R1@ represents, Y2 represents, and m and n each represent an integer of 1 to 1o. Rll+R, , R, , R141, , R, and Ro each represent a hydrogen atom, an alkyl group, an acyl group, or an alkyl group, and Ro is -NR1, R□.

-OR, ffi or -5Jz, R2° and R11
each represents a hydrogen atom or an alkyl group, and R12 represents an atomic group necessary for bonding with R4 to form a ring.

R□. Alternatively, R11 may be combined with Ro to form a ring. M' represents a hydrogen atom or a cation.

-Formation [■] In the formula, Ar represents an arylene group or a divalent organic group containing an arylene group, B2 and B each represent an alkylene group, and R! 3. R, , Rss and R1° each represent a hydroxy-substituted alkyl group, and X and y each represent O or l. G' represents anion, 2 is 0
, l or 2.

-Formation (III In the formula, R2F and R1 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, RSS represents a hydrogen atom or an alkyl group, and R3° represents a hydrogen atom or a carboxyl group. .

-Formation [X] In the formula, 2, . 2. 2 and Z each represent a carbon atom or a nitrogen atom, and at least among them, R11 and R12 each represent a hydrogen atom or a substituent.

General formula [■] In the formula, R, 3, R3, R, and R36 each represent a hydrogen atom or a substituent.

General formula (Xln) arSAg In the formula, R1 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 may have a substituent. .

In the general formula CI), the heterocycle formed by Q and the heterocycle represented by R4 are each a fused heterocycle (
For example, 5- to 6-membered unsaturated rings are fused).
The alkyl group represented by 1 preferably has 1 to 5 carbon atoms. Further, the heterocycle formed by Q and each group represented by R include those having a substituent (for example, an alkyl group, a carboxyl group, a sulfo group, an acyl group, etc.).

- In formation (n), the heterocycle formed by Q contains a fused heterocycle (for example, one in which 5- to 6-membered unsaturated rings are fused), and a substituent (for example, an alkyl group, an aryl group, Carboxyalkyl group, alkoxycarbonylalkyl group, halogen atom, vinyl group, anilino group,
acylamino group, sulfonamide group, etc.).

-Formation (I [I), the alkyl group represented by R2, R3+ R'' and the alkylene group represented by B each preferably have 1 to 6 carbon atoms, and the acyl group represented by R2゜R3 preferably has 2 to 4 carbon atoms.

In addition, the heterocyclic group represented by A and R" is a fused heterocyclic group (
For example, R
Each group represented by z, Rs, A and R" includes those having a substituent (eg, hydroxyl group, alkyl group, etc.).

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

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

In the general formula (VT), the hydrocarbon chains represented by D, ~D, may be saturated or unsaturated, for example, 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 formation [■], R11 to R18 + R2°.

The alkyl group represented by R2 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.
Examples of the divalent organic group containing an arylene group include combinations of an arylene group and an alkylene group and/or a hetero atom (for example, an oxygen atom).

Bs, alkylene group represented by Bs and R2s to R26
The hydroxy-substituted alkyl group represented by is preferably one having 1 to 6 carbon atoms.

- Formation (X)1. j-i ite, Z +, Z 2. Z
When s or 2° 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) .

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

In the general formula [■], examples of the substituents represented by R13 to R3g 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 (xm), 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,
Examples thereof include an ammonium group, an alkoxy group, a sulfonyl group, a sulfo group, an acyl group, a thioacyl group, a carbamoyl group, a thiocarbamoyl group, and a 5Rsa group (R3 represents a hydrogen atom or a silver atom).

The compounds of the present invention represented by the above-formation CI) to (XII[) can be represented as (BA).Ag.

Representative specific examples of the compound [BA) and the compound represented by the above-mentioned -formation CXm] are listed below, but the invention is not limited thereto.

Exemplary compound ( ■ ) ( ■ -2) ( ■ -3) ( ■ 4) ( ■ -5) ( -6) CH2C)I, C0OH ( ■ -7) ( ■ -8) shtl, 1y112L, υυh (I -9) shinns ( ■ -11) (tl-1) (II-3) ([[-5) (■ 11O) (ff-2) (Il-4) (I[-6) (■ 7) (II-9) (n-11) (II-13) (II-15) (n-8) (II-10) (If -12) (I[-14) (U-16) (n-17) (n -19) (U-21) (II-’23) (III-1) (n -18) (n -20) (n-22) (m-2) (III-3) (I[l- 4) (II[-5) (I[[-6) H,N-C3NHNHC3-NH.

(II[-7) HJ-CSNH(CHi)zNHcs NH2(II
I-8) (I[[-9) (1111-10) (■ 11) (I[[-12) (m -13) (nl-14) (I[[-17) ([1-18) (III -19) (I[[-20) (I[+ -22) ) (III -21) (DI -23) (Ill -25) (■ 26) (m -27) (rV-1) CH .

(Vl-2) CH3 (■ 3) CH.

CH.

CH3 (V - ) (V -2) (V -3) (Vl- ) (Vl-2) (VT -3) (VT-4) (VI-5) (Vl-6) (Vl -7) ( Vl -10) I'1M (Vl -13) (VI -16) (Vl-8) (Vl-9) (VI -11) (vt -12) (VI -14) (Vl -15) (Vl - 17) (■-1) (■-2) (■-3) (■-4) (■-5) (■-7) (■-8) (■-9) (■-10) (■- 11) (■-12) (■-1) (■-2) (■-3) (■-4) (■-5) (■-6) CHtNH(C)lxcHzOH)i (■-7) ( II- ■ ) ■ (ff -3) ([-5) (II-2) (II-4) (X-1) (X-3) CX-S > (n-) (XI-3) (X -2) (X-4) (X-6) (II-2) (U-4) (n-5) (I[-) (■-3) (]OI-5) (Xll-7) ( U-6) (ff-2) (Xll-4) (XM-6) (XI[-8) XII[- NH! -CH, CH, -SAg XII[-2 X■ - X■ - HOOCCHzCH* SAg XI[[-5 xm - m-7 xm xm [[-14 C,H,C00H XII[-15 XI[[-16 XII[-17 XnI -18 Xllr -19 XI[[-20 XI[l-22 Xm-27 XI[[-30 XI[1-31 Xm-32 nl-34 XIII-33 x■-35 Xm-36 Xm-37 XI[l-39 l-40 0OC CH,CHzSCH,CH2SAg mm-4 2HOOC-CHzCHzOC)12CI(2SAm-
43 Xm-44 XIII-45 Xm-47 (Jl, OCH, CHzCSAg XI[l-49 XI[l-50

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. 3,779,75
The silver salt of the present invention, which can be easily synthesized by the known technique described in No. 7, No. 3,893.858, etc., is
It 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.

11? = Surveying Ha, Photosensitive material M l m'Tada') I
X 10-4 to 100 g is preferred, especially l X 10
-' to Ig are 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 a-genin-3-acetic acid (1-2) was mixed with 200 g of a-genin-3-acetic acid (1-2).
It was dissolved in 0a+Q water, and 169 g of a 10% silver nitrate aqueous solution was added over 15 minutes. After further stirring for 2 hours, the white crystals formed were collected by filtration, washed with 2000 mg of 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 I-2)
, 5% Alkanol XC (manufactured by DuPont) 10mff
and 300 m<1 of water were added and dispersed in a ball mill for 12 hours to obtain a dispersion.

Synthesis of silver salt of compound-2 31 g of 4-sulfobenzotriazole (n-2) was mixed with 1
Dissolved in 000aIQ water, IO% 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 tQ 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, 10 mff of 5% alkanol xC (manufactured by DuPont) and 400 g of water
m12 was added and dispersed in a ball mill for 12 hours to obtain a milky white dispersion.

The silver halide emulsion used in the present invention is any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

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

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 coupling a colored coupler with a competitive coupler having a color correction effect and an oxidized form of a developing agent, it can be used as a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, and a fogging agent. agents, antifoggants, chemical sensitizers,
Compounds that release photographically useful fragments such as spectral sensitizers and desensitizers can be used.

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 commonly used as cyan dye-forming couplers.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalesian layer, an antiirradiation 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 the development process.

A formalin scavenger-1 optical brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a color capri-preventing agent, a development accelerator, a development retardant and a bleach accelerator can be added to the photosensitive material.

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 - washing with water (2) color development - bleach-fixing - one small amount of water washing, one washing with water (3) color development → bleach-fixing → washing with water → stable (4) color development → bleach-fixing - stable (5) color development - Bleach fixing Ichisho 1 stable - M2 stable (6)
Color development - washing with water → bleach-fixing - washing with water (7) color development → bleaching acceleration - bleach-fixing - stable (8) color development - bleaching acceleration → bleach-fixing → washing with water (9) color development - pre-fixing → bleach-fixing - stable (
10) Color development - pre-fixing - bleaching - stable (11) Color development → bleaching → water washing constant fixing - water washing → stable (12) color development → bleaching constant fixing - water washing → stable (13) color development → bleaching → fixing →
1st stable → 2nd stable color development → bleaching - small amount of water washing → fixing - small amount of water washing 1 water washing - stable (15) Color development → bleaching → bleach fixing - 1st stable → 2nd stable color development - bleaching acceleration - bleaching constant fixing → First stabilization → Second stable color development → Small amount of water washing → Bleach → Small amount of water washing → Fixing - Small amount of water washing Depressed water washing → Stable color development - Bleaching acceleration - Bleaching - Small amount of water washing Constant fixing - Small amount of water washing → Water washing → Stable black and white development → Water washing (or stable) - h reversal → color development - constant bleaching, one water wash (or omitted) black and white development - water washing (or stable) - reversal → color development → bleach acceleration → bleach → fixing → water washing (or omitted) - stable black and white development - Water washing (or stable) - Reversal → Color development - Bleach fixing - Water washing (or omitted) - Stable (22) Black and white development → Water washing (
or stable) → reversal → color development - bleaching acceleration → bleach-fix constant fixing → washing with water (or omitted) → stable (20) (21) (14) (16) (17) (18) (19) In addition, in the above steps A bleach 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.),
In addition to the ferric complex salts of aminopolycarboxylic acids such as the ferric complex salts of ethylenediaminetetraacetic acid (described in Japanese Patent Publication Nos. 58-11617 and 53-11818), particularly preferable examples include A ferric rust salt of the aminopolycarboxylic acid shown below.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'.triacetic acid [4]] 1.3-diaminopropanetetraacetic acid 5] Triethylenetetraminehexaacetic acid [6] Cyclohexanediaminetetraacetic acid [711,2-diaminopropanetetraacetic acid [8] 1.3-
Diaminopropan-2-ol-2-tetraacetic acid [9] Ethyl etherdiaminetetraacetic acid [101 Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetraprobionic acid [12] Phenylenediaminetetraacetic acid [13] Disodium ethylenediaminetetraacetic acid salt [14
] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16]
1 Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid sodium salt [8]
Sodium pyrenediaminetetraacetic acid salt [19J Ethylenediaminetetramethylenephosphonic acid [20] Sodium cyclohexanediaminetetraacetic acid salt [211 Diethylenetriaminepentamethylenephosphonic acid [221 Cyclohexanediaminetetramethylenephosphonic acid] [231 Nitrilotriacetic acid [24] Iminoniacetic acid [ 25] Hydroxyethyliminodiacetic acid [26] Nitrilotripropionic acid [27] Nitrilotrimethylenephosphonic acid [28] Iminodimethylenephosphonic acid [29] Hydroxyethyliminodimethylenephosphonic acid [30] Nitrilotriacetic acid trisodium 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, diethylenetriamine [
, 1,3-diaminopropanetetraacetic acid, 112-diaminopropanetetraacetic acid, 1,4-diaminobutanetetraacetic acid, glycol etherdiaminetetraacetic acid and cyclohexanediaminetetraacetic acid, particularly preferably diethylenetriaminepentaacetic acid, 1.3 -diaminopropanetetraacetic acid.

Ferric complex salts of aminopolycarboxylic acids can be used as free acid hydrogen salts, alkali metal salts such as sodium salts, potassium salts, and lithium salts, or 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, the working liquid 112
It can be used in an amount of 0.01 mol or more, preferably 0.0
It is used in an amount of 5 to 0.8 mol.

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) A multilayer color photosensitive material sample No. 1 having a multilayer structure having the following composition was placed on a subbed cellulose acetate support.
“No.32 was created.

Coating amounts are expressed in units of g/W2 in terms of silver for silver halides and colloidal silver, and in g/lx'' for additives and gelatin. The 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 (listed in Table 1) are added to the first layer in the form of a dispersion or an aqueous solution. 3 mmol/II2 was added to (DC).

The emulsion contained in each color-sensitive emulsion layer is optimally sensitized using sodium thiosulfate and chloroauric acid. 01 ( H Y-1 CM-1 Q -1 H Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye V Hardener H- ■ S-1 H Below, each layer of the above composition is HC, IL-1 described above.

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

They shall be indicated by the abbreviations B-1, B-2, Pro-1, and Pro-2.

In addition to the above 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 Table 1
Description established
Wash with water for 6 minutes and 30 seconds
Stabilized 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, flEa salt 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 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 1-0g
Add water to make a tela. (p)l-10,02) Bleach solution (formulation A) Ethylenediaminetetraacetic acid iron(III) Ammonium salt 100.0g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150.0° Glacial acetic acid
Add 10.0 g of water to make H, and adjust the pH to 6.0 using aqueous ammonia.

Bleach solution (formulation B) 1.3-diaminopropane tetraacetic acid iron (m) ammonium salt 180.0 g 1.3-diaminopropane tetraacetate iron (m) ammonium salt 4.0 g ammonium bromide 128.0 g ammonium nitrate 1 g, 0 g glacial acetic acid
69.0g ammonium water (25
%) Add 30Q water to make 112, and adjust to pH 4.5 using ammonia water.

Fixing solution Ammonium thiosulfate 175.0g Anhydrous ammonium sulfite 8.6g Sodium metaviLrIi 2.3g Add water to make lα,
Adjust to pf (6,0) using acetic acid.

Stabilizing liquid formalin (37% aqueous solution) 1, 5
+aI2 Konidax (manufactured by Funica Co., Ltd.) 7
．． Add 5mff water to make 112.

Next, the same samples 1 to 32 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 Used in each processing step; The composition of the processing solution is shown below.

Color developer: Same bleach-fix solution as above Ethylenediaminetetraacetic acid Strict iron (III) Ammonium 80.0g Ethylenediaminetetraacetic acid ammonium salt 3.0g Ammonium thiosulfate (70% solution) 13Q, 0wN Ammonium sulfite (40% solution) 27 .5mff
Add 100.0 m4 of the above color developer to bring the total volume to IQ, 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, the red light sensitivity of each sample and the graininess of the red light sensitive layer (RM
S value) was calculated.

That is, each sample was subjected to wedge exposure according to a conventional method, and the same process as above was performed except that the bleaching process was performed with bleaching solution (A) for 6 minutes and 30 seconds. The optical density with red light was measured using a meter PDA-65, and the sensitivity was calculated from the exposure amount necessary to give an optical density of 0.5 J, and the sensitivity was calculated as a relative value with the value of sample N001 as 100. Indicated.

The RMS value is measured using a microdecimometer with a circular scanning aperture of 25 µm through a red filter at the minimum density + 1.2.
The value of the standard deviation of the variation in the concentration value that occurs when scanning with a scanner was determined and expressed as a relative value with the value of sample N001 set as 100.

As is clear from Table 1, Sample No. 2 containing the silver salt of the present invention has excellent desilvering properties, but has a large deterioration in graininess. In contrast, samples No. 4 to No. 3 containing the silver salt of the present invention and the DSR compound of the present invention
In Sample No. 2, a significant improvement in graininess was observed, and an improvement in sensitivity was also observed.

〔Effect of the invention〕

As is clear from the above results, according to the present invention, it was possible to provide a silver halide color photographic material that has good desilvering properties, can be processed rapidly, has high sensitivity, and has excellent graininess.

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 the light-sensitive silver halide emulsion layers contains a compound capable of reacting with an oxidation product of a color developing agent to scavenge the oxide or a compound capable of releasing a precursor thereof; A silver halide color photographic light-sensitive material characterized in that at least one of the photographic constituent layers contains a silver salt of a compound having a bleaching accelerating effect.