JPH03255441A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure superior sharpness and graininess and to reduce a change of photographic performance with the lapse of time from photographing (exposure) to development by forming at least one silver halide emulsion layer on a base and incorporating a specified compd. CONSTITUTION:At least one silver halide emulsion layer is formed on a base and a compd. represented by formula I is incorporated. In the formula I, A is a residue of a coupler other than 1H-pyrazolo-[1,5-b]-1,2,4-triazole and 1H- pyrazolo[5,1-c]-1,2,4-triazole, L1 is a group represented by formula II, etc., L2 is a group releasing INH-(CH2)n-Q by electron transfer along the conjugated system, INH is a residue of a development inhibitor bonding to L2 through a hetero atom, n is an integer of 0-3 and Q is a group having 80-250 mol. wt. Superior graininess and sharpness are ensured and a change of photographic performance due to heat and moisture with the lapse of time from exposure to development can be reduced.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a silver halide color containing a novel compound capable of releasing a development inhibitor having an excellent development inhibitory ability at an appropriate timing during development processing. It relates to photographic materials.

(Prior art) In recent years, silver halide photosensitive materials, especially color photosensitive materials, have been developed using l50, which has a high image quality comparable to Is○ sensitivity 100.
There has been a demand for a photosensitive material with high sensitivity, excellent graininess and sharpness, and excellent storage stability, such as 400 photosensitive material (Super HG-400).

As a compound that improves sharpness but does not deteriorate the storage stability of sensitive materials, a compound that releases a development inhibitor imagewise via two or more timing groups is disclosed in, for example, JP-A-60
-218645, 60-249148, 61-
No. 156,127 and US Pat. No. 1,086,1701. However, these compounds have insufficient improvement in sharpness and graininess because the rate (timing) of releasing the development inhibitor is inappropriate or the diffusivity of the development inhibitor is too large. Furthermore, many of the sensitive materials containing these compounds have the problem of increased fog and significant decrease in sensitivity when left for a long period of time after exposure to development or when exposed to high temperature and high humidity conditions.

Recently, a European patent has been published for a coupler that can improve sharpness without increasing the interimage effect by changing the structure of the development inhibitor to a specific coupler that releases the development inhibitor through a timing group. It was disclosed in No. 348139. It is true that these couplers have made it possible to improve sharpness to some extent, but even with these couplers, it is not easy to control the release rate of the development inhibitor, so the improvement in sharpness is not sufficient. There were problems such as large fluctuations in photographic performance due to time, temperature, and humidity.

(Problems to be Solved by the Invention) The purpose of the present invention is to propose a silver halide color photographic light-sensitive material that has excellent sharpness and graininess and has little fluctuation in photographic properties over time from photographing (exposure) to development. It is to be.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, a compound represented by the following general formula (I). This was achieved by a silver halide color photographic light-sensitive material characterized by containing.

General formula (I) %formula%) In the formula, A is 1H-pyrazolo(I,5-b)-1°2.4
-triazole and 1H-pyrazolo[51-c]-1
, represents a coupler residue other than 2,4-triazole,
Ll represents -W-C-1 or R1□-0-C-.

1 Here, W represents an oxygen atom, a sulfur atom, or a tertiary atom group, and R11 and R1! independently represent a hydrogen atom or a substituent. L2 represents a group that releases INH-(CL), -Q by electron transfer along the conjugated system, and IN
H represents a development inhibitor residue bonded to L2 through a heteroatom, n represents an integer from O to 3, and Q represents a molecular weight of 80
represents a group of from 250 to 250.

In general formula (I), A is 1H-pyrazolo (I, 5,
Represents a coupler residue other than -1,2,4-triazole and 1H-pyrazolo(5,1-tech)-1,2,4-triazole.

For example, yellow coupler residues (e.g., closed ketomethylene type), magenta coupler residues (5-pyrazolone type, pyrazoloimidazole type, etc.), cyan coupler residues (phenol type, naphthol type, etc.), and colorless coupler residues ( Indanone type, acetophenone type, etc.). Also, U.S. Patent No. 4,315,070, U.S. Patent No. 4.
It may also be a heteroprototypical coupler residue as described in No. 183752, No. 3,961,959 or No. 4°171.223.

Preferred examples of six are the following formulas (Cp-1), (Cp~2
), (Cp-3), (Cp-6), (Cp-7), (C
p-8), (Cp-9), or (Cp-10). These couplers are preferred because of their high coupling speed.

General formula (Cp-1)00 111 Rs +CCHCNH-Rsz RstNHCCH(CNH)bRss -Formula (Cp-3) General formula (Cp-9J General formula (Cp-10) 1ss General formula (CP-6) H General formula ( Cp-7) General formula (Cp-8) 0)1 In the above formula, the free bond derived from the campling position represents the bonding position of the campling leaving group.

In the above formula, Rsrs Rsz, R5I, Rsa, R5
When S, R511% Raa, R6゜, R1, R62 or R63 contains a diffusion-resistant group, it means that the total number of carbon atoms is 8
40 to 40, preferably 10 to 30; otherwise, the total number of carbon atoms is preferably 15 or less. In the case of bis-type, telomer-type or polymer-type couplers, any of the above-mentioned substituents represents a divalent group and connects repeating units and the like. In this case, the range of carbon numbers may be outside the specified range.

R5I to R5S, R6, to R63, b, d, and e will be explained in detail below. In the following, R□ represents an aliphatic group, an aromatic group, or a heterocyclic group, R4□ represents an aromatic group or a heterocyclic group, and R45, R44, and R4, represent a hydrogen atom, an aliphatic group, an aromatic group, or Represents a heterocyclic group.

R5I has the same meaning as R4I, b is 0 or 1
R5t and R5i each have the same meaning as R4□, R64 is a group that has the same meaning as R□, R,, C0N
- group, R□N- group, R,, SO2N- group, Ras
R43Ra3 R□S- group, R,30- group, R=sNCON- group, or R
42Raa or NIC- group. R5S represents a group having the same meaning as R41. Rsa represents the same group as Ral,
R1, is a group having the same meaning as R41, R4IC0N- group, 0 R=+0CON- group, R,, So, N- group, Ras
Ra3 R,, NC0N- group, R,, O- group, R,, S- group, haR44R4S halogen atom, or R,, N- group. d represents O43 or 3. When d is plural, the plural R59's represent the same W substituent or different substituents. Moreover, each R59 may become a divalent group and connect to form a cyclic structure. An example of a divalent group for forming a cyclic structure is Ra3 Ra3. Here, f represents an integer from 0 to 4, and g represents an integer from O to 2, respectively.

R5° represents a group having the same meaning as R41. R1 is R4,
A group with the same meaning as Ro, Raz is a group with the same meaning as Ro, R4+
0CONH~ group, R,, SO, NH- group, R,, NC0
N- group, R,, NSO2N- group, Rat R4S
R44R45R430 - group, RoS- group, halogen atom or R,, N- group, R43 is a group with the same meaning as R□, Ro R,, SO, N- group, R,, NSO, - group, R44R4
4 R,,SO,- group, R,,0CO- group, R,,0-3o
, - group, halogen atom, nitro group, cyano group or R1
Represents a C0- group. e represents an integer from 0 to 4. When there is a plurality of Rhz or R61, each represents the same or different thing.

In the above, the aliphatic group is a saturated or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. Representative examples include methyl, ethyl, propyl, isopropyl, butyl, (I)-butyl, (I)-butyl,
(I)-amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,3.3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

The aromatic group is preferably a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted naphthyl group.

A heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, preferably a 3- to 8-membered ring selected from a nitrogen atom, an oxygen atom, or a sulfur atom. It is.

Representative examples of heterocyclic groups include 2-pyridyl, 2-thienyl, 2-furyl, 13,4-thiadiazol-2-yl, 2,4-dioxo-1,3-imidazolidine-5-
yl, 1.2.4-triazol-2-yl or ]-
Examples include pyrazolyl.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include a halogen atom, R,, O- group, R,, S- group, RntCON- group, R
,,NGO- group,R,,0CONR,,R,@R,F group,R,,SO,N- group,R,,NSO,- group,Rat
Rag R,, SO2- group, R,,0CO- group, R,,NC0N
- group, a group having the same meaning as R46, Ra5Ra* υ group, cyano group, or nitro group. Here R4
& represents an aliphatic group, an aromatic group, or a heterocyclic group, and R
at, Ram and Raw are each an aliphatic group, an aromatic group,
Represents a heterocyclic group or a hydrogen atom. Aliphatic, aromatic or heterocyclic have the same meanings as defined above.

Next, preferred ranges of Rs+ to Rsss Rsw to Rhx, d, and e will be explained.

Rat is preferably an aliphatic group or an aromatic group.

Rat, Rss and Rss are preferably aromatic groups.

Preferably, R2 is an aliphatic group or an aromatic group. - In formula (Cp-6), R59 is a chlorine atom,
An aliphatic group or an R□C0NH- group is preferred. d is preferably 1 or 2. R60 is preferably an aromatic group, - In formula (Cp-7), RB is Ra + CON H-
Groups are preferred. - In formula (Cp-7), d is preferably 1. R1 is preferably an aliphatic group or an aromatic group.

- In formula (Cp-8), e is preferably 0 or 1, R42 is R410CONH- group, R, IC0N
H- group or R, SO, NH- group is preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring. - Formula (C
In p-9), Ru3 is R,, C0NH- group,
R,, So□NH- group, R,, NSO,- group, 0 R41S○,- group, R,, NGO- group, nitro group or 4
3 is preferably a cyano group.

In general formula (Cp-10), Ruff is A3 R,, NGO- group, R,, CCO- group or R,, CO
One R41 group is preferred.

Next, a typical example of R, + to R55s Rs* to R1 will be explained.

Rs+ includes (I)-butyl group, 4-methoxyphenyl group, phenyl group, 3-(2(2,4-di-t-amylphenoxy)butanamido)phenyl group, or methyl group aR5! and R83 is a phenyl group, 2-chloro-5-ethoxy group, 2-chloro-5-ethoxy group,
-dodecyloxycarbonylphenyl group, 2-chloro-
5-hexatecylsulfonamidophenyl group, 2-chloro-5-tetradecanamidophenyl group, 2-chloro-
5-(4-(2,4-di-t-adanylphenoxy)butanamido)phenyl group, 2-chloro-5-(2-(2,
4-di-t-amylphenoxy)butanamido)phenyl group, 2-methoxyphenyl group, 2-methoxy-5-tetradecyloxycarbonylphenyl group, 2-chloro-
5-(I-ethoxycarbonylethoxycarponyl)phenyl group, 2-pyridyl group, 2-chloro-5-octyloxycarbonylphenyl group, 2,4-dichlorophenyl i, 2-chloro-5-(I-dodecyloxycarbonylethoxy carbonyl) phenyl group, 2-chlorophenyl group or 2-ethoxyphenyl group.

As Rsa, butanoylamino group, 2-chloro-3
-propanoylaminoanilino group, 3-(2-(2,4
-di-t-amylphenoxy)butanamido)benzamide group, 3- (4-(2゜4-di-t-amylphenoxy)butanamido)benzamide group, 2-chloro-5
-tetradecanamide aniline group, 5-(2,4-di-
t-amylphenoxyacetamido)benzamide group,
2-chloro-5-dodecenylsuccinimideanilino group, 2-chloro-5-(2-(3-t-butyl4-hydroxyphenoxy)tetradecanamide)anilino group, 2
．． Examples of eR8s include 2-dimethylpropanamide group, 2-(3-pentadecylphenoxy)butanamide group, pyrrolidino group, or N,N-dibutylamino group, 2,4゜6-dolichlorophenyl L 2-chlorophenyl 1 .2.5-dichlorophenyl group, 2.3-dichlorophenyl &, 2.6-dichloro-4-methoxyphenyl group, 4-(2-(2,4-di-t-amylphenoxy)butanamido)phenyl group or 2 .6-dichloro-4-methanesulfonylphenyl group is a preferred example.

R5I includes 2-chlorophenyl group, pentafluorophenyl group, heptafluoropropyl group, 1-(2,4
-di-t-amylphenoxy)propyl group, 3- (2
,4-di-monoamylphenoxy)propyl group, 2,4
-di-t-amylmethyl group or furyl group. R2 is a chlorine atom, a methyl group, an ethyl group,
Propyl group, butyl group, isopropyl group, 2-(2,4
-di-t-adanylphenoxy)butanamide group, 2(2
, 4-di-t-amylphenoxy)hexane ado group,
2-(2,4-di-t-octylphenoxy)octanamide group, 2-(2-chlorophenoxy)tetradecanamide group, 2-(4-(4-hydroxyphenylsulfonyl)phenoxy)tetradecanamide group, or 2
- (2-(2,4-di-t-amylphenoxyacetamido)phenoxy)butanamide group.

R1° is a 4-cyanophenyl group, 2-cyanophenyl 1.4-butylsulfonylphenyl group, 4-propylsulfonylphenyl group, 4-chloro3-cyanophenyl group, 4-ethoxycarbonylphenyl group, or 3.
A 4-dichlorophenyl group is mentioned. As R1,
Propyl group, 2-methoxyphenyl group, dodecyl group, hexadecyl group, cyclohexyl group, 1-(2,4-di-
t-amylphenoxy)propyl group, 4-(2,4-di-t-amylphenoxy)butyl group, 3-dodecyloxypropyl group, t-butyl group, 2-methoxyl 5-dodecyloxycarbonylphenyl group, or 1 -naphthyl group. Examples of Rh* include isobutyloxycarbonylamino group, engineered toxycarbonylamino group, phenylsulfonylamino group, methanesulfonamide group, benzamide group, trifluoroacetamide group, 3-phenylureido group, butoxycarbonylamino group, or acetamide group. It will be done. As R&3, 24-di-t-amylphenoxyacetamide group, 2-(2,4
-di-L-alkylphenoxy)butanamide group, hexadecylsulfonamide group, N-methyl-N-octadecylsulfamoyl group, N,N-dioctylsulfamoyl group, 4-t octylhendiyl group, dodecyl- quincarbonyl group, chlorine atom, nitro group, cyano group, N-
(4-<2.4-di-L-amylphenoxy)methyl)
Examples include carbamoyl group, N-3-(2,4-di-t-amylphenoxy)propylsulfamoyl group, methanesulfonyl group, and hexadecylsulfonyl group.

In general formula (I), the group represented by L+ is *-〇-
It is a group represented by C-** or the following general 2 (T-I). Here, * represents the bonding position with A of the compound represented by the general formula (I), and ** represents the bonding position with the beam.

- Formula (T-1) * -W-C-Kimoto 12 In the formula, W represents an oxygen atom, a sulfur atom or a -N- group, R8 and RIK represent a hydrogen atom or a substituent, and R13 represents a substituent represents.

When Rlr and RIK represent a substituent and RIf
Typical examples of f are RIS group, R, Co- group, RI
SSO! - group, R,, NC〇- group, or R 6 R,, N S ox- group. Here, R1 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R16 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.

RI 1% A case where each of R12 and RI3 represents a divalent group and is linked to form a cyclic structure is also included. - Specific examples of the group represented by formula (T-1) include the following groups.

CH.

Among these, one or both of RII and RIK is more preferably a hydrogen atom.

In the general formula (I), the group represented by L2 represents a group that causes a cleavage reaction using an electron transfer reaction along a conjugated system, and is described in, for example, U.S. Pat. No. 845, JP-A-57-188035,
It is described in No. 5B-98728, No. 5B-209736, No. 58-209737, No. 5B-209738, etc., and is a group represented by the following formula (T-2).

-Formula (T-2) C) I, CHff In the formula, W, Rlr and Rlr have the same meanings as (T-1), and * indicates the position bonded to the porcelain in general formula (I). represents the bonding position with INH→CH,h,Q; however, R1, and R,t may be bonded to form a benzene ring or a heterocycle, and Ro or R1
! and W may be combined to form a heterocycle.

Further, Zl and 22 each independently represent a carbon atom or a nitrogen atom, and X and y represent O or 1. When ZI is a carbon atom, X is 1, and when ZI is a nitrogen atom, χ is 0
It is. The relationship between z2 and y is also the same as the relationship between Zl and X. Also, t represents 1 or 2, and when t is 2, the two Z+ = Zr- may be the same or different (R,,),
(R+z)y Good.

Preferred specific examples of (T-2) are listed below.

*-Q, , CH・-゛・ Among these, those that bond to Ll through nitrogen atoms are more preferable.

In the compound represented by the general formula (I), the group represented by TNH is a development inhibitor residue bonded to L2 through a heteroatom, and is preferably the following formula (INH-1) to (IN
H-12).

(INH-1) (INH-2) ([NH 6) (INH In the formula, R0 is a hydrogen atom or a substituted or unsubstituted hydrocarbon group (e.g. methyl, ethyl, propyl, phenyl)
represents.

(INH-7) (INH-4) (INH-5) (TNH-8) (INH-9) (INH 10) (INH-11) (INH-12) In the formula, * is represented by general formula (I). The group represented by L2 of the compound represented by ** represents the bonding position with the group represented by -(ctiz>-Q).

Among these, (INH-1) is preferable as INH.
, (INH-2), (INH-3) (INH-4) and (TNH-12), particularly preferably (INH-
1) and (INH-3).

The group represented by Q in the compound represented by general formula (I) has a molecular weight of 80 to 250, preferably 90 to 2
00, particularly preferably from 100 to 150.

! 4. Physically, when n of the compound represented by general formula (I) is 0, Q is a substituted or unsubstituted α-branched alkyl group (e.g. 2-hexyl, 2-octyl, t-octyl,
2-decyl, 2-dodecyl), aryl groups with electron-donating groups (e.g. p-methoxyphenyl, p-tolyl)
and when n is 1 or more, Q is an alkyl group (e.g. hexyl, octyl, t-octyl, decyl, dodecyl)
, acylamino groups (e.g. benzamide, hexaneamide), alkoxy groups (e.g. octyloxybenzyloxy), sulfonamide groups (e.g. pentanesulfonamide, P-toluenesulfonamide), aryl groups (e.g. P-methoxyphenyl, P-dimethylaminophenyl, P-ethylphenyl), alkylthio groups (e.g. hexylthio, octylthio), alkylamino groups (e.g. dibutylamino, piperidino), alkoxycarbonyl groups (e.g. butoxycarbonyl, hexylcarbonyl), acyloxy groups (e.g. butanoyl) oxy, benzoyloxy), sulfonyl groups (e.g. butanesulfonyl, benzenesulfonyl), aryloxy groups (e.g. phenoxy, p-)lyloxy, p-methoxyphenoxy), carbamoyl groups (e.g. dipropylcarbamoyl,
phenylmethylcarbamoyl) sulfamoyl group (e.g. dimethylsulfamoyl, diethylsulfamoyl)
, nitro, cyano or aryloxycarbonyl group (eg phenoxycarbonyl, 4-methoxyphenoxycarbonyl). However, Q may be further substituted with a substitutable group.

n is preferably O to 2, particularly preferably O or 1. Further, when n is O, Q is preferably an aryl group having an electron donating group.

Further, when n is 1 or more, Q is preferably an alkoxy group, an aryl group, or an aryloxy group. Particularly preferably, n is l and Q is an aryl group.

/ / / / /' Specific examples of the compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.

(Exemplary compound) (I) H2 Indicates that it is bonded to -CH2- at the 1st position.

The same applies to the following cases. ) (2) (3) (7) 11 Ul　ICO□C2H3 (4) H (8) H (:H2 C2H5 (I0) 0H (I1) (I4) (I5) 2H5 (I2) C5H (I1 α (I7) (I8) α (I9) α (22) υ C wealth 0 (23) H C wealth 0 (20) α ρ, H2 (24) B CI(.

HI (′.

υshi II words (26) (30) H 01’1 C.B.

CHC(hcHs L (29) 0)1 H2 C.B.

(34) 0H Hz (35) R 1h (38) H υ C=0 H2 (36) H (37) H C! +0 (40) FI υ C! 0 (41) H Shire 3 Shith (42) OH (44) OH -0 (43) OH (45) OH υ C Tsumugi O C=0 The compound of the present invention is disclosed in JP-A-60 No. 218645 The bottom can be made according to the method described in et al.

Exemplified compound (I) below and (37) specific of Here is an example of a bottom.

(Combined example I) 1a of aH OH2 f 1b (4- or 5-hydroxymethylimidazole hydrochloride, 13.4 g) in thionyl chloride (30 μl)
．． It was refluxed for 5 hours. After thionyl chloride was distilled off under reduced pressure, methylene chloride (40 μl) was added, and the solvent was distilled off under reduced pressure. The crude crystals obtained in this way were used as Ib (22.2 g)
and diisopropylethylamine (25.8 g) in DMF
The mixture was added to the solution (60 μl) and reacted for 2 hours. The water was drained and the precipitated crystals were collected to obtain 30 g of 1c.

Synthesis of Id lc (30 g) and 37% formalin aqueous solution (22°5-
1) was reacted in acetic acid (80 Preparation 1) at 80°C for 2 hours.

After the solvent was distilled off under reduced pressure, thionyl chloride (30 ml) was added and the mixture was reacted under reflux for 2 hours. After removing excess thionyl chloride under reduced pressure, ether was added to obtain 32 g of 1d as crude crystals.

6 g of sodium hydride (60%, oil dispersion) was added to a DMF (301 Ill) solution of the platform 1e (I0, 2 g) of 1r. ld (I9 g) was added thereto and reacted for 3 hours. IN
The mixture was made acidic by adding hydrochloric acid and extracted with chloroform. The extract was washed with water, dried over vL# sodium, and condensed to obtain an oil.

This was purified by silica gel column chromatography using chloroform-MeOH (5:1) as an eluent to obtain 5.2 g of If.

If (5,2 g) and Ig (3,1 g) of ethyl acetate (3
0 steel 1) suspension for 1 h (2,1 g> of ethyl acetate (6 m
l) 1 liquid and N,N-dimethylaminopyridine (0.1g
) was added and reacted overnight. After the precipitated crystals were separated, the oral fluid was concentrated. The obtained oil was purified by silica gel column chromatography (ethyl acetate-hexane 1:2) to obtain 1 as crude crystals. The structure of 1 was confirmed by giving M"=805 by mass spectroscopy. After stirring 2b (I0 mmol) and 2c (I0 mmol) in methylene chloride (4(I+1) for 1 hour, 2a (
Add a solution of 10gaol) in ethyl acetate (40e+1), and then add diisopropylethylamine (20wool).
was added and stirred for 1 hour. After stopping the reaction by adding 2N hydrochloric acid (20s+l) and water (50s+l), methylene chloride (4(
The organic layer was washed three times with water. The organic layer was dried over anhydrous sodium sulfate and concentrated, and the resulting residue was subjected to mass spectrometry to give an exemplary compound (M''=847) (
37) was confirmed.

Although the compound represented by the general formula (I) of the present invention may be used in any layer in the light-sensitive material, it is preferably added to the light-sensitive silver halide emulsion layer and/or its adjacent layer. It is more preferably added to an emulsion layer, and particularly preferably added to a red-sensitive silver halide emulsion layer.

The total amount of these compounds added to the photosensitive material is usually 3×1
0-' to 1×10-O1/1, preferably 3X
10-' to 5 X 10-' mol 7m'', more preferably IX ] 0-' to 2 X 10-' so
l/*”.

The compound represented by the general formula (I) of the present invention can be added to a light-sensitive material in the same manner as a conventional coupler, as described below.

/ The light-sensitive material of the present invention may be provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. The number and order of the emulsion layers and non-photosensitive layers are especially f! A typical example is a halogen compound having at least one photosensitive layer on a support from a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. It is a silver halide photographic light-sensitive material, and the light-sensitive layer is a unit light-sensitive layer that is sensitive to blue light, green light, or red light.In multilayer silver halide color photographic light-sensitive materials, generally The unit photosensitive layers are arranged in this order from the support side: a red sensitive layer, a green sensitive layer, and a blue sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121.470 or British Patent No. 923.045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support: low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (G) I) / low sensitivity green sensitive layer ( GL)/
High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL)
) or BH/BL/GL/GO/R11/RL
(7)R.

Alternatively, they can be installed in the order of Bll/BL/GK/GL/RL/R11.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer /cH/R
They can also be arranged in the order of H/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/FIL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is distributed, and the photosensitivity decreases sequentially toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4,663゜2
No. 71, No. 4,705,744, No. 4,707.
No. 436, JP-A-62-160448, JP-A No. 63-89
A multilayer effect donor layer (CL) having a different spectral sensitivity distribution from the main photosensitive layers such as BL, GL, and RL as described in the specification of No. 850 is arranged adjacent to or close to the main photosensitive layer IF''
It is preferable to do so.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) Nα17643
(December 1978), pp. 22-23, “1. Emulsion preparation
d types)'', same 18716 (I979 1
January), 648 pages, Doketsu 307105 (November 1989)
), pp. 863-865, and the graphic ``Physics and Chemistry of Photography'', 1 volume, published by Montell (P, Glafki
des, Che@ie et Pb1sique P
photographique+ Paul Monte
Duffin, "Photographic Emulsion Chemistry", published by Focal Press (G.F. Duffin, 1967).

Photographic Emulsion Che
mistry (Focal Press1966
)'), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al.
Published by Focal Press (V, L, Zelikman
etal、Making and Coating
Photographic Emulsion, F
ocal Press, 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engtnering), No. 1431N, pp. 248-257 (I970); Rice! iI
easily by the methods described in Patent No. 4,434,226, Patent No. 4,414.310, Patent No. 4,433.048, Patent No. 4,439,520, British Patent No. 2.112.157, etc. It can be made by TW.

The crystal structure may be --like, the inside and outside may have different halide compositions, it may be a layered structure, or silver halides of different compositions may be joined by epitaxial bonding. The particles may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide, or a mixture of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. The additives used in such processes are Research Disclosure 1--?
h 17643, k 18716, and FkX3
07105, and the relevant parts are summarized in the table below.

In the present invention, it is preferable to use non-light-sensitive fine-grain silver halide. Non-light-sensitive fine-grain silver halide is not exposed to light during imagewise exposure to obtain a dye image, but is not exposed to light during the development process. These are fine silver halide grains that are not substantially developed and are preferably not fogged in advance.

The fine-grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and/or silver iodide as necessary, preferably silver iodide in a content of 0.5 to 100 mol%. It contains 10 mol%.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of the projected area) of 0.01 to 0.5 μm, and 0.01 to 0.5 μm.
02 to 0.2 μm is more preferable.

Fine-grain silver halide can be produced in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, it is preferable to add in advance a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound, or a zinc compound.

Known photographic additives that can be used in the present invention are also described in the three Research Disclosures mentioned above, and the relevant descriptions are shown in the table below.

In addition, in order to prevent the deterioration of photographic performance due to formaldehyde gas, US Patent No. 4,411,987 and US Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 4,435.503.

Various color couplers can be used in the present invention, and specific examples thereof include the aforementioned Research Disclosure Ko 17643, ■-C-G, and the same 307105,
■It is described in the patent described in -〇-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4.022,620, No. 4.3
No. 26,024, No. 4,401,752, No. 4,
248,961, Japanese Patent Publication No. 5B-10739, British Patent No. 1.425,020, British Patent No. 1.476.760, U.S. Patent No. 3.973.968, British Patent No. 4.314.
No. 023, No. 4,511.649, European Patent No. 24
No. 9,473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
0.619, European Patent No. 4,351,897, European Patent No. 73,636, US Patent No. 3,061,432, European Patent No. 3725.067, Research Disclosure I 24220 (June 1984) , JP-A-60-33
No. 552, Research Disclosure Nα2423
0 (June 1984), Japanese Patent Publication No. 60-43659,
No. 61-72238, No. 60-35730, No. 55
-118034, US Patent No. 60-185951, US Patent No. 4.500.630, US Pat.
No. 4.556,630, International Publication No. 10881047
Particularly preferred are those described in No. 95 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4.052.212.
No. 4,146,396, No. 4,228.23
No. 3, No. 4,296,200, No. 2.369.9
No. 29, No. 2,801, No. 171, No. 2,772.
No. 162, No. 2,895,826, No. 3,772
．． No. 002, No. 3.758.308, No. 4,33
No. 4.011, No. 4,327,173, West German Patent Publication No. 3゜329.729, European Patent No. 121,365
No. ^, No. 249°453A, U.S. Patent No. 3.446
, No. 622, No. 4,333,999, No. 4,77
No. 5,616, No. 4,451,559, No. 4,4
No. 27,767, No. 4,690,889, No. 4
, 254.

No. 212, No. 4,296.199, JP-A-61-4
Those described in No. 2658 and the like are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820; 4,080,211; 4,367.282;
No. 4.576°910, British Patent No. 2.102.
No. 137, European Patent No. 341°188A, etc.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, EP 96,570 and DE 3,234,533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure Seed 17643.
-G term, ■-G term of NcL307105, U.S. Patent No. 4.163.670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4.004.929, No. 4,138.25
No. 8, preferred is that described in British Patent No. 1,146,368, and correction of unwanted absorption of the chromogenic dye by the fluorescent dye released upon coupling as described in U.S. Pat. No. 4,774,181. Coupler, U.S. Patent Nos. 4 and 7
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with the developed leaves to form a dye as described in No. 77.120.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. In addition to the DIR couplers of the present invention, the DIR couplers releasing development inhibitors include the above-mentioned ilD 17643, ■-F section and ilD k 3071.
05, the patent described in section ■-F, JP-A-57-15
No. 1944, No. 57-154234, No. 60-184
No. 248, No. 63-37346, No. 63-37350
No. 4,248.962, U.S. Patent No. 4,782,0
Those described in No. 12 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
2.13i, No. 188, JP-A-59-157638
No. 59-170840 is preferred.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , the multi-equivalent couplers described in JP-A-60-185950, etc.
DIR redox compound releasing coupler, DIR coupler releasing coupler, D as described in JP-A-62-24252 etc.
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173.30
R, D, NCL 1144, a coupler that releases a dye that recolors after separation, as described in No. 2^, No. 313,308A.
9, No. 24241, bleach accelerator-releasing couplers described in JP-A-61-201247, etc., U.S. Pat. No. 4,555,
Ligand-releasing coupler described in No. 477, etc., JP-A-63
Couplers that release leuco dyes as described in US Pat. No. 4,757,181 and couplers that release fluorescent dyes as described in US Pat.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point f@ media used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-1-amylphenyl) isophthalate, bis(I,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid. Esters (triphenyl phosphate, tricresyl phosphate, 2
-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl, p-hydroxybenzoate, etc.), Amide I (N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone) etc.), alcohols or phenols (isostearyl alcohol,
, 4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters II (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (ll , N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like.

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Examples include 2-ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation can be found in U.S. Pat. etc. are listed.

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiaprin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5 described in JP-A-1-80941
-dimethylphenol, 2-phenoxyethanol, 2
- It is preferable to add various preservatives or antifungal agents such as (4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the R
D, page 28 of Shame 17643, page 647 right column to page 648 left column of Doibei 18716, and page 87 of 307105.
It is described on page 9.

In the light-sensitive material of the present invention, the total thickness of the entire aqueous colloid layer on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and 16 μm or less. It is particularly preferable that the membrane swelling rate TI/□ is 30 seconds or less, more preferably 20 seconds or less.
2 days), and the membrane swelling rate T I/l
can be measured according to techniques known in the art, e.g., Nee-Green (A, Green
Photogr, Sci, Eng
), 19@, No. 2, pages 124-129, it can be measured by using a swellometer (swelling membrane), and TI/□ can be measured using a color developer at 30'C for 3 minutes and 15 seconds. The saturated film thickness is defined as 90% of the maximum swollen film thickness reached during treatment, and is defined as the time required to reach 1/2 of the saturated film thickness.

The membrane swelling rate T, 78 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling rate is preferably 150 to 400%.11 The swelling rate can be calculated from the maximum swollen film thickness under the conditions described above according to the formula = (maximum swollen film thickness - film thickness) / film thickness. .

The color photographic material according to the present invention is described in the above-mentioned RD, pages 28-29 of Tane 17643, 651 left column to right column of RD 18716, and pages 880-881 of RD 18716, 651.
It can be developed by the usual method described in the page.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-NN diethylaniline, 3-methyl-4 -amino-N-ethyl-N-β
-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and sulfates thereof, Examples include hydrochloride and p-toluenesulfonate. Among these, in particular, 3-methyl, 4. Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred, and two or more of these compounds may be used in combination depending on the purpose.

Color developers include pelt buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It typically contains an inhibitor or antifoggant. In addition, if necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, tta salt, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, ethylene glycol, etc. , alkaline solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-
Auxiliary development fresh leaves such as phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N , N,N-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains di-hydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black and white developing raw chestnuts such as 3-pyrazolidone M such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but -a is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the amount of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all processes such as bleaching, bleach-fixing, fixing, washing, and stabilization, and it is also possible to reduce the amount of replenishment by using means to suppress the accumulation of bromide ions in the developer. .

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pi and using a color developing agent at a straw concentration.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (Iff), peracids, quinones, nitro compounds, etc. Typical bleaching agents include iron (III) compounds, etc.
i salts, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraferoic acid, or citric acid, tartaric acid, malic acid Complex salts such as can be used. Among these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetate iron (Ifti salt) and 1,3-diaminopropanetetraacetate iron (I[[)if salt) are useful for rapid processing and prevention of environmental pollution. Aminopolycarboxylic acid iron (III) complex salts are preferred from the viewpoint of the above, and are particularly useful in both bleaching solutions and bleach-fixing solutions. pH of liquid
is usually 4.0 to 8, but it is also possible to process at an even lower pH to speed up the process.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in JP-A No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. 81117129 (July 1978), etc.; JP-A-50-140129 Thiazolidine derivatives described in Japanese Patent Publication No. 45-8506, JP-A-52-20832, JP-A-53-32735, U.S. Patent No. 3,706.56
Thiourea derivative described in No. 1; West German Patent No. 1.127□
No. 715, iodide salts described in JP-A No. 5846.235; West German Patent Nos. 966.410 and 2,748,430
Polyoxyethylene compounds described in the No.: Special Publication No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-40.943, 49-59.644, 53-
No. 94.927, No. 54-35.727, No. 55-2
Compounds described in No. 6,506, No. 58-163, and No. 940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893.85.
No. 8, West German Patent No. 1.290.812, Japanese Unexamined Patent Publication No. 1983-
Preferably, the compounds described in U.S. Pat. No. 95,630 are preferred, and the compounds described in U.S. Pat. These bleach accelerators are particularly effective when bleach-fixing materials.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain a II acid for the purpose of preventing bleach staining.
is 2 to 5, specifically acetic acid, propionic acid, etc. are preferable.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or bleach-fixing solution has pHt
! A compound having a pKa of 6.0 to 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole, is added at 0.1 to 0 mol/l for control. It is preferable to do so.

The total time for the desilvering process is preferably as short as possible without causing derailment, preferably from 1 minute to 3 minutes, more preferably from 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C to 45°C. In a preferred temperature range, the derailment speed is improved and the occurrence of staining after treatment is effectively prevented.

In the desilvering process, it is preferable to strengthen the stirring as much as possible.A specific method for strengthening the stirring is to impinge a jet of processing liquid on the emulsion surface of a photosensitive material as described in JP-A-62-183460. Method and JP-A-62-183
No. 461 is a method of increasing the stirring effect using a rotating means, and furthermore, the stirring effect is further improved by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of the cleanser and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used, such as photocoupler), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urn-al of tbeSociety of M
tion Ptcture and Te1e-vi
sion EngiIlleers Volume 64, P, 2
48-253 (May 1955 issue),
You can ask for it.

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, the following problems arise:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8.542
Isothiazolone compounds, thiabendazole Enoki, chlorinated disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (I986), Sankyo Publishing, Hygiene Technical Association, “Microbial sterilization, sterilization, and anti-mildew technology (I982),” Industrial Technology Association, Japan Society of Anti-Mold Control, “Dictionary of antibacterial and anti-mildew agents” (I9
The fungicides described in 1986) can also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is in the range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out; an example of this is a stabilization bath containing a dye stabilizer and a different activator, which is used as a final bath for color photographic materials. Examples of dye stabilizers that can be used include aldehydes such as formalin and glutaraldehyde, H-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. Example U.S. Patent No. 3.342.59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure +-NCL14,
Ship base type compounds described in No. 850 and No. 1115,159, Fuldol compounds described in No. 13.924, metal salt complexes described in U.S. Pat. Examples include type compounds.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
Various processing solutions in the present invention described in No. 144547 and No. 58 to 115438 are 10°C to 50°C.
Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate the processing and shorten the processing time, or conversely, lower temperatures can be used to improve MW and stabilize the processing solution. Improve your sexuality! ! can be admonished.

Further, the silver halide photosensitive material of the present invention is disclosed in US Patent No. 4.
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

(Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example: On a subbed cellulose triacetate film support,
M! as shown below! ! Sample 101, which is a multilayer color photosensitive material consisting of each layer, was prepared.

(!!A optical layer set Fg) Coating amounts are in g/rt of silver for silver halides and colloidal silver, and in g/rd for coupler additives and gelatin. and, for sensitizing dyes, halogenation in the same layer [expressed in moles per mole].

1st layer (antihalation layer) Black colloid go, is gelatin 1.00ExM-80
,02 2nd layer (intermediate layer) Gelatin V-1 V-2 V-3 xF-1 Solv-'1 'i43 layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 2 mol%, internal high Agl type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin crystal mixed particle, diameter/thickness ratio 2.5)! ! ! Cloth silver amount
0.45 gelatin 1.
0ExS-11,oxlo-'ExS-23,0XIO-'EXS-31,0XIO-' ExC-30,22 ExC-40,010 Solv-10,007 4th layer (mid-sensitivity red-sensitive emulsion layer) Iodobromide Silver emulsion CAgT 4 mol%, internal height 1.20 0, 03 0, 06 0, 07 0, OO4 0, 07 AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of 1 sphere equivalent diameter 20%, normal crystal, twin crystals Mixed particles, diameter/thickness ratio 1)
Coated silver amount 0.80 gelatin
1.05ExS-11,0XIO-'ExS-23,0XIO-'ExS-31,0XIO-' ExC-30,33 ExC-40,005 ExY-140,008 ExY-130,02 ExC-20,08 Cpd- 101,0xlO-' 5olv-10,10 5th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 19 %, twinned mixed particles, diameter/thickness ratio 6) Coated silver amount 0.60 Gelatin 0.90EχS-
11,0XIO-'ExS-23,oxio-'ExS-31,0XIO"' ExC-50,07 EχC-60,08 Solv-10,15 Solv-20,08 m1!6 layer (middle layer) Gelatin 0. 60P-20,
05 Cpd-10,10 Cpd-40,17 Solv-10,05 7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 12 mol%, internal high Agl type, sphere equivalent diameter 0.3 μm, sphere Coefficient of variation of equivalent diameter 28%, normal crystal,
Twinned mixed grains, diameter/thickness ratio 2.5) Coated silver amount
0.30 gelatin 0.4
0ExS-45,0xlO-'ExS-60,3X10-'ExS-52,oxlo-' ExM-9o, 2 ExY-130,03 ExM-80,03 Solv-10,2 8th layer (medium-sensitivity green-sensitive emulsion Layer) Silver iodobromide emulsion (AgI 4 mol%, internal high Agl type,
Equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 4) Coated silver amount
0.65 gelatin 0.9
0ExS-45,oxio-'ExS-52,0XIO-'ExS-60,3X10-' ExM-90,25 ExM-80,03 ExM-100,015 ExY-f3 0.04Solv
-10,2 'J! 9 layers (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10 mol%, internal high Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, normal crystal, twin mixed grains, Diameter/thickness ratio 2.0)! ! Coated silver amount 0.50 gelatin
O,5OExS-42,oxxo-'ExS-52,0xlO-'ExS-60,2XIO-' ExS-73,0XIO°4 ExM-110,06 ExM-120,02 ExM-80,02 Cpd-20,01 Cpd-92,0XIO-'Cpd-102,0xlO-' 5olv-10,20 Solv-20,05 m1!10 layer (yellow filter layer) gelatin
0.55 yellow colloid g
o, osCpd-10,18 Solv-10,15 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, internal high Agl type, equivalent sphere diameter 0.5 μm, equivalent sphere diameter Coefficient of variation 15%, octahedral particles) Coated silver amount 0.35 Gelatin 1. OEχS-8
2.0 Type, equivalent sphere diameter 1.3 μm, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twin crystal mixed grains, diameter/thickness ratio 4.5) Coated silver amount 0.45 gelatin
0.500XIO-' 0.12 0.001 2.0X10"' 0,04 ExS-81゜xY-15 Cpd-2 cp d-5 olv-1 13th layer (first protective layer) Fine grain silver iodobromide (Average particle size 0.07 μm, Ag 11 mol%) 0.17 gelatin
0.8UV-20,l UV-30,l UV-40,2 Solv-30,04 14th layer (second protective layer) Gelatin polymethyl methacrylate particles (diameter 1.5μm) 0.18H-1
0,35 Furthermore, in order to improve storage stability, processability, pressure resistance, anti-mold and antibacterial properties, antistatic properties, and applicability, Cpd-3, cp d-5, and Cpd described in 0,70 below are added. -6, Cpd-
7, Cp d-8, P-1, P-2, W-1, W-2,
W-3 was added and the above 14 layers were coated simultaneously. The dry film thickness was 16.2 μm.

(Sample iox~///n Sample ioi was prepared by adding a comparison coupler RC-/1 of 0.0 19/rn to the third layer of sample ioi and O1Oφ01/m2 to the φth layer.

Sample 10 was replaced with the RC-/'i comparison compound of sample 102 and the compound represented by general formula (I) of the present invention.
3~/// were produced. The types and amounts of added compounds (RC-i'6i, o in molar ratio) are shown in Table/. The amounts of these additions were set so that the gamma (gradation) almost matched.

These samples were imagewise exposed to white light and subjected to the following color development process. The excellent photographic performance obtained is shown in Table 1 along with the RMS value indicating granularity (value of cyan image with an aperture of at μm diameter). Sharpness was also measured using the conventional MTF method after the same processing. Furthermore, after carrying out the same imagewise exposure with the above-mentioned white light, it was left to stand for 1ψ days under the forced condition of ur0c relative humidity of 10%, and then the same development process was carried out. After imagewise exposure through a red filter (5C-42 manufactured by Fuji Film), a uniform exposure of 0.orcMs was performed using a green filter (BPN-4'j manufactured by Fuji Film).
Shimamitsu Nanagyo's development process, cyan density/,! It is shown in Table 2 as @gold turbidity, which is obtained by subtracting the magenta density at the cyan fog density from the magenta density at .

The color development process was carried out using an automatic developing machine at 300C as described below.

Color development in 3 minutes! Bleach for 1 minute Bleach feet W 3 minutes/! Wash for seconds ■ Wash for φO seconds ■ Stable for 7 minutes Dry for seconds Dry (zo'c) i minute l! Sec. In the above treatment steps, a countercurrent water washing method was used, from ① to ②, and from ② to ②. Next, the composition of each treatment liquid will be described.

The replenishment amount of each processing solution was 7,200 m for color development per m of color photosensitive material, and for all other processes including washing with water.

Also, the amount of pre-bath carried into the washing process is per m2 of color photosensitive material! It was Od.

(Color developer) diethylenetriaminepentaacetic acid/-hydroxyethylidene/,/-diphosphonate sodium sulfite potassium bromide potassium iodide hydroxylamine sulfate p-(N-ethyl-N-β-hydroxyethylamino)-co Add methylaniline sulfate solution to pH Mother liquor /, Og ko, Og a, og 3o, og /, ψg /, 3 dako, φg ge, !g /, 01 10.0 Replenisher /, 7g 2.29 ≠, ψg 3, Og 0.79 1, g z, op / , 01 10.0! (Bleach solution) Common to mother liquor and replenisher: ethylenediamine/ferric ammonium tetraacetate /20.Oji ethylenediaminetetraacetic acid disodium salt io, og ammonium nitrate io, og ammonium bromide / 00, 09 bleach accelerator
Add J-X10-3 mol ammonia water
pHt・3 water t-X
/-01 <Bleach constant N solution> Ethylenediaminetetraacetic acid ferric ammonium salt common to mother solution and replenisher to, og ethylenediaminetetraacetic acid disodium salt! -09 Sodium sulfite/co, OI ammonium thiosulfate aqueous solution (yoog/l) Cog0rttl Add aqueous ammonia p)l 7. Add J water /l (washing water) Calcium ion 32■/l, Magnesium ion 7.
Tap water containing 3 da/l was passed through a column filled with an H-type acidic cation/exchange resin and an OH-type strong basic anion exchange resin, and calcium ions were 1.2/l and magnesium ion was 0. It was used by adding 20,119 grams per tii of sodium incyanurate dichloride to water treated on September 1, 2013.

Stabilizing solution> Mother solution/replenisher common formalin (J 7% w/v) 2, 0ml
Polyoxyethylene-p-monononylphenyl ether 0.31! iI (Average degree of polymerization 10) Ethylenediaminetetraacetic acid di-sodium salt 0, Og9 water was added and dried at 1 MHz.The drying temperature was RO 0C.

From Table 1, it can be seen that the samples of the present invention had a value of 11, which kept the change in color turbidity small, and the sharpness expressed by MTF value and RMS
Excellent graininess expressed in value, and et 'c, to%
It is clear that there is little variation in photographic properties under severe conditions.

Example 2 The compounds of the present invention, vtnro, oizi/m2, and 0.05% were added to the φth layer and the first layer of sample ior of JP-A No. 2003/02000/0. Sample 20/ was prepared by adding OC#j9/m2. Samples 202 to 204 were prepared in the same manner, and t00μm
Xucm and/! Soft X@ was irradiated through an aperture of .mu.m x .mu.cm, and the edge effect was measured by measuring the cyan coloring density at the center of each. The results are shown in Table 2. From Table 2, it can be seen that the samples of the present invention clearly have excellent edge effects and excellent 'r, that is, excellent sharpness.

For development, an automatic cine processor was used for the processing steps and processing solution compositions shown below.

However, the samples to be evaluated for performance were subjected to imagewise exposure in a case in which the cumulative replenishment amount of the color developing solution was three times the volume of the mother solution tank, and then the samples were processed.

Processing process Processing time Processing temperature Replenishment amount "Color development"
3 minutes/! Seconds 3r, 00C2Jnt bleach
jO seconds 31.00Cjm! Bleach RN 60 seconds 3lr, 0'C feet arrived! O seconds 3r,
ooc 1trtte water wash (I) 3o seconds
j r, 0'C water washing (2+ 20 seconds 31
-0'C: jutn! Cheap foot 20 seconds 3r,
Dry at 0°C 20rnl for 7 minutes! ! 0C Replenishment amount is J! Amount per mm width/m Water flow is countercurrent from (2) to (I1), and all the overflow of the washing water is introduced into the fixing bath.The bleach-fixing bath is refilled using the bleaching method of the automatic processor. The upper part of the tank and the bottom of the bleach-fixing tank and the upper part of the fixing tank and the bleach-fixing tank are connected with pipes, and all the overflow liquid generated from the supply of replenisher to the bleaching tank and fixing tank □ is transferred to the bleach-fixing bath. In addition, the amount of developer brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach constant W solution brought into the fixing process, and the amount of fixing solution brought into the washing process. The amount to bring is 3!mm width of photosensitive material/m length, respectively.
! Id, 2-0 door 1.2.0ml, 2. It was tNd. The cross-over time is 1 second, and this time is included in the processing time of the previous step. For each processing bath, a method was used in which a jet of each processing solution was made to collide with the emulsion surface of the sensitive material using the method disclosed in Japanese Patent Application Laid-open No. 1997-13-13.

The composition of the treatment liquid is shown below.

(Developer solution) Mother solution (J) Replenisher G) Diethylenetriamine, 0 2.2 Pentaacetic acid l-Hydroxyacetic acid Li 3.3 3.3 Den-l,/-Sodium sulfite diphosphonate 3.2 Potassium dicarbonate 37 ．． ! J, O Potassium bromide /, ≠ O1 ← Potassium iodide hydroxylamine sulfate 2-methyl-≠-[N-ethyl-N-(β-hydroxyethyl) Add aminocoaniline sulfate solution to pH (bleaching solution) l , 3-propylenediaminetetranodic acid ferric ammonium-hydrochloride ammonium bromide ammonium nitrate hydroxyacetic acid Add acetic acid water l+31n9 2+guda,! 3.3 6, / /, Ol /, 01 10, Oj 10,1! Mother liquor) Complementary solution G) lφg, 0 20bu, 2 ra,.

/7. ! BuJ, 0 33, l /, OJl /20.0 2j, 0 ri 0.0 17, F 1, θ1 pH (ammonia water CJ, 20 2. IO adjustment) (Bleach-fixing solution mother liquor) With the above bleaching solution mother liquor A mixture of 1! and 1j of the following fixer mother liquor (fixer) Mother liquor (b) Replenisher (b) Replenisher solution (7001/l) Imidazole 2r,! Ethylenediamine tetranodic acid 12. ! Add water and i, ol pH7, ψO [Adjusted with aqueous ammonia and acetic acid] (Washing water) Common tap water for mother liquor and replenisher 'fI: H-type strong acidic strength Strongly acidic cation exchange resin Amberlite IR- manufactured by Andhaas Co., Ltd. t2゜B) and O
H-type strongly basic anion exchange resin (Amberlite IR)
A-4AOO) t-filled mixture! 7.0/ri,σ! ! ,! 37,! /, 01 7, ←! tg0rnl koIOm! Water is passed through the bed type column to reduce the concentration of calcium and magnesium ions to 3■/j! The following treatment was followed by sodium incyanurate dichloride 2θ da/l and sodium sulfate l!
θη/It addition a.

The pH of this liquid was in the range of j, r-7, j.

(Stable solution) Common to mother solution and replenisher solution (Unit I) E/?
Phosphorus (37%) 2.0ml polyoxyethylene-p-O, J Monononylphenyl nityl (average degree of polymerization 10) 5olv-1 Tricresyl diphosphate 5olv-2: Dibutyl phthalate 5olv-3 Tri(2- (ethylhexyl) ExF-1: ExC-2: Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

UV-4: ExC-5: ExM-8: ExY-14: ExY-15= CH.

ExM-11: ExS-3: ExS-4: ExS-5: EXS-6: ExS-7: CCHz) a SOi Na p d-7 p d-8 p d-9 cpa-i.

-2 Js -3 CsF+JOJ(CJt)CHtO)OI[-1 Copolymer ratio of vinylpyrrolidone and vinyl alcohol -70=30 direct weight)-2 Polyethyl acrylate ExS-8: H-1: CHt -CH-3ot CHz CONH-CHzC
Ht-CH-3Ch-CHg-CONH-CHlCpd
-3: Cpd-4: 0[1 Cpd-5: Cpd-6 RC-φ (U.S. Patent No. φ, (Compound 5 of Ti70/No. 5) α RC-1 (European Patent Publication No. 311!, No./3) FLC-/(JP-A-60-U/F41J Coupler
(I9)) α C-J (Coupler (26) of JP-A-4/-/JT/27) R (Knee 2 (Coupler (I) of JP-A-40-2112/φ) Example 3 Compounds (I), (3), and (7) of the present invention were added to the third layer of the sample/θl of JP-A No.
o-'moA! /m2, and the same eggplant test as in Example 1 was carried out, and it was confirmed that by adding the compound of the present invention, a photosensitive material with excellent graininess, sharpness, and photosensitive material storage stability could be obtained. Ta.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer provided on a support, characterized in that it contains a compound represented by the following general formula (I). Silver chemical color photographic material. General formula (I) A-L_1-L_2-INH-(CH_2)_n-Q in the formula, A is 1H-pyrazolo[1,5-\b\]-1,2,
4-triazole and 1H-pyrazolo[5,1-￥c
￥] - Represents a coupler residue other than 1,2,4-triazole, and L_1 has ▲ mathematical formula, chemical formula, table, etc. ▼,
Or ▲ represents a mathematical formula, chemical formula, table, etc. ▼. Here, W represents an oxygen atom, a sulfur atom, or a tertiary amino group, and R_1_1 and R_1_2 independently represent a hydrogen atom or a substituent. L_2 represents a group that releases INH-(CH_2)_n-Q by electron transfer along the conjugated system, INH represents a development inhibitor residue bonded to L_2 through a heteroatom, and n is an integer from 0 to 3. , and Q represents a group having a molecular weight of 80 to 250.