JPH0540331A - Silver halide color photographic sensitive material and method for processing same - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material superior in color reproduction performance and sharpness. CONSTITUTION:The silver halide color photographic sensitive material has at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support, and it contains a coupler represented by formula I, when the thickness of dried film is <=22mum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, a photographic light-sensitive material, which contains a novel development inhibitor and is remarkably excellent in sharpness, rapid processing property, color reproducibility and desilvering property. And a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material, especially a color light-sensitive material for photographing, has good color reproducibility and sharpness, can shorten development processing time, and is excellent in desilvering property. Is required.

Means for improving color reproducibility and sharpness are disclosed in JP-A-51-146828 and JP-A-60-2186.
No. 45, No. 61-156127, No. 63-37346.
No. 1, JP-A 1-280755 and 1-219747.
No. 2-230139, European Patent Publication 348.
There are known couplers which release a development-inhibiting compound described in JP-A-139, JP-A-354532 and JP-A-403019, via two timing groups. Certainly, by using these timing DIR couplers, the interlayer effect and the edge effect were improved and the color reproducibility and the sharpness were improved to some extent, but the release of the development inhibitor was substantially further, or The effect was still unsatisfactory due to unfavorable timing of release. Further, the photosensitive materials using these compounds have problems that the desilvering property is poor and that the photographic properties are greatly changed due to changes in the processing liquid composition and processing time.

On the other hand, a light-sensitive material having a thin dry film is described and proposed in JP-A-61-173248 and JP-A-63-166334, and a light-sensitive material having a small silver content is JP-A-62-89963. No. 63-226651, JP-A No. 2-19842, No. 2-20859, and No. 2-2.
However, since these compounds do not use the compound of the present invention, they have drawbacks such as poor color reproducibility and sharpness and low density in short-time development processing.

[0005]

An object of the present invention is to firstly provide a light-sensitive material excellent in color reproducibility and sharpness, and secondly to have sufficient color forming property even in a short-time development processing. The third object is to provide a light-sensitive material, and thirdly to provide a light-sensitive material having a small amount of residual silver even in a short time desilvering process and having suitability for a short time.

[0006]

The above problems have been solved by the following halogen-colored silver photographic light-sensitive material.

(1) Halogen having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer on a support and having a dry film thickness of 22 μm or less. A silver halide color photographic light-sensitive material, comprising a coupler represented by the general formula (I) shown in the following chemical formula 3 and / or the general formula (II) shown in the following chemical formula 4 material.

[0008]

[Chemical 3] (In the general formula (I), A represents a coupler residue or a redox group, L ₁ and L ₃ represent a divalent timing group, and L ₂ represents a trivalent or higher-valent timing group. , PUG represents a photographically useful group.j
And n each independently represent 0, 1 or 2, and m is 1
Alternatively, 2 is represented and s is a number obtained by subtracting 1 from the valence of L ₂ and represents an integer of 2 or more. Also, L ₁ , L ₂ or L ₃
When a plurality of are present in the molecule, they may all be the same or different. Also, there are multiple PUGs
May all be the same or different. )

[0009]

[Chemical 4] (In formula (II), A and PUG are as defined in the general formula (I) .L ₄ is -OCO- group ,, - OSO group, -OSO ₂
- group -, - group - OCS- group, SCO-group, -SCS- group or -WCR ₁₁ R _12. Where W is an oxygen atom,
Represents a sulfur atom or a tertiary amino group (—NR ₁₃ —),
R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a substituent, and R ₁₃ represents a substituent. In addition, each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and includes a case where they are linked to each other to form a cyclic structure. L ₅ represents a group that releases PUG by electron transfer along a conjugated system or a group defined by L ₄ . (2) A and P in the general formula (I) and the general formula (II)
The formula weight of the residue excluding the group represented by UG is 64 or more 240
The silver halide color photographic light-sensitive material as described in (1) above, which is:

(3) The halogen according to (1) or (2) above, wherein the total silver content of the photographic light-sensitive material is 1.0 g / m ² or more and 4.9 g / m ² or less. Silver halide color photographic light-sensitive material.

(4) The specific photographic sensitivity of the photographic light-sensitive material is 80.
The silver halide color photographic light-sensitive material as described in (1) or (3) above, which is at least 800.

(5) The silver halide color photographic light-sensitive material described in any of (1) to (4) above is subjected to color development processing containing an aromatic primary amine developing agent, desilvering processing, and then washed with water. And / or a color processing step of performing stabilizing processing, wherein the processing time of the color developing step is 150 seconds or less.

Below, the general formula (I) and the general formula (II)
The compound represented by will be described in detail.

In the general formula (I), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (eg, open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide), magenta coupler residues (eg 5-pyrazolone type, pyrazolo). Coupler residues such as triazole type or imidazopyrazole type), cyan coupler residues (eg phenol type, naphthol type, imidazole type described in EP-A-249,453, or pyrazolo type described in 304,001). Pyrimidine-type coupler residues) and achromatic coupler residues (eg, imidanone-type or acetophenone-type coupler residues). Also, U.S. Pat. No. 4,315,0
No. 70, No. 4,183,752, No. 4,174,96
No. 9, No. 3,961,959, No. 4,171,223
Or a heterocyclic coupler residue described in JP-A No. 52-82423.

When A represents a redox group, the redox group is a group which can be cross-oxidized by an oxidized product of a developing agent, and examples thereof include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1 , 2-naphthohydroquinones, sulfonamide phenols,
Examples include hydrazides or sulfonamide naphthols. These groups are specifically described in, for example, JP-A-61-1
230135, 62-2251746, 61-2
78852, U.S. Pat. Nos. 3,364,022, 3,379,529, 3,639,417, 4,684,604 or J. Org. Chem. ，
29, 588 (1964).

Preferable examples of A include general formulas (Cp-1), (Cp-2) and (Cp-
3), (Cp-4), (Cp-5), (Cp-6),
(Cp-7), (Cp-8), (Cp-9), (Cp-
10) or a coupler residue represented by (Cp-11). These couplers are preferred because of their high coupling speed.

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8] In the above formula, the * mark derived from the coupling position is L ₁ or less in the general formula (I) and the general formula (II)
Represents a bonding position with a group of L ₄ or less.

In the above equation, R₅₁, R₅₂, R₅₃, R₅₄,
R₅₆, R₅₇, R₅₈, R₅₉, R₆₀, R ₆₁, R₆₂, R₆₃, R
₆₄Or R₆₅If contains a non-diffusible group, it is
The number will be 8-40, preferably 10-30
Otherwise, the total number of carbon atoms is 15 or more.
Lower is preferred.

R _{51 to} R ₆₅ , k, d, e and f will be described in detail below. In the following, R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₄₂ represents an aromatic group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic group or an aromatic group. Represents a group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ each have the same meaning as R ₄₂ . k represents 0 or 1. R ₅₄ represents a group having the same meaning as R _41, R ₄₁ CON
(R ₄₃ ) -group, R ₄₁ R ₄₃ N-group, R ₄₁ SO ₂ N (R ₄₃ ).
-Group, R ₄₁ S- group, R ₄₃ O- group, R ₄₅ N (R ₄₃ ) CON
(R ₄₄ )-group or ::: C-group. R ₅₅ is R ₄₁
Represents a group having the same meaning as. R ₅₆ and R ₅₇ are each R ₄₃
A group having the same meaning as a group, R ₄₁ S-group, R ₄₃ O-group, R ₄₁ CO
It represents an N (R ₄₃ )-group or an R ₄₁ SO ₂ N (R ₄₃ )-group. R ₅₈ represents a group having the same meaning as R ₄₁ . R ₅₉ is R ₄₁
A group having the same meaning as R ₄₁ CON (R ₄₃ ) -group, R ₄₁ OCO
N (R ₄₃ )-group, R ₄₁ SO ₂ N (R ₄₃ )-group, R ₄₃ R ₄₄
NCON (R ₄₅₎ - represents group R ₄₁ O-group, R ₄₁ S- group, a halogen atom or R ₄₁ R ₄₃ N- group. d represents 0 to 3. When d is plural, plural R _59's represent the same or different substituents. Also, each R
₅₉ may be a divalent group and connected to each other to form a cyclic structure.
Examples of forming a cyclic structure include forming a pyridine ring or a pyrrole ring. R ₆₀
Represents a group having the same meaning as R ₄₁ . R ₆₁ represents a group having the same meaning as R ₄₁ . R ₆₂ is a group of the same meaning as R _41, R ₄₁ OCO
NH- group, R ₄₁ SO ₂ NH- group, R ₄₃ R ₄₄ NCON (R
₄₅ ) -group, R ₄₃ RNSO ₂ N (R ₄₅ ) -group, R ₄₃ O-
Represents a group, R ₄₁ S-group, halogen atom or R ₄₁ R ₄₃ N-group. R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₃ CON
(R ₄₅ )-group, R ₄₃ R ₄₄ NCO- group, R ₄₁ SO ₂ N (R
₄₄ ) -group, R ₄₃ R ₄₄ NSO ₂ — group, R ₄₁ SO ₂ — group, R
_{It represents a 43} OCO- group, an R ₄₃ O-SO ₂ -group, a halogen atom, a nitro group, a cyano group or an R ₄₃ CO- group. e is 0
Represents an integer of 4 to 4. When there are a plurality of R ₆₂ or R ₆₃ , these represent the same or different. R ₆₄ and R ₆₅ are respectively R ₄₃ R ₄₄ NCO— group, R ₄₁
CO-group, R ₄₃ R ₄₄ NSO ₂ -group, R ₄₁ OCO-group, R
_{41 represents a} SO ₂ — group, a nitro group or a cyano group. Z ₁
A nitrogen atom or = C (R ₆₆₎ - represents a group (R ₆₆ is a group of the same meaning as a hydrogen atom or R _63). Z ₂ represents a sulfur atom or an oxygen atom. f represents 0 or 1.

In the above, the aliphatic group has 1 to 3 carbon atoms.
2, preferably 1 to 22 saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group. Representative examples are methyl, ethyl, propyl, isopropyl, butyl, (t) -butyl, (i) -butyl, (t) -amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,
Examples include 3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

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

The heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, and a hetero atom selected from a nitrogen atom, an oxygen atom or a sulfur atom, preferably a substituted or unsubstituted 3- to 8-membered ring. Is a heterocyclic group. Typical examples of the heterocyclic group are 2-pyridyl, 2-furyl, 2-imidazolyl, 1-indolyl, 2,4-dioxo-1,3.
-Imidazolidin-5-yl, 2-benzoxazolyl, 1,2,4-triazol-3-yl or 4-pyrazolyl.

The above-mentioned aliphatic hydrocarbon group, aromatic group and compound
When the cyclic group has a substituent, as a typical substituent
Is a halogen atom, R₄₇O-group, R₄₆S-group, R₄₇CO
N (R₄₈) -Group, R₄₇N (R₄₈) CO- group, R₄₆OCO
N (R₄₇) -Group, R₄₆SO₂N (R₄₇) -Group, R₄₇R₄₈
NSO₂-Group, R₄₆SO₂-Group, R₄₇OCO- group, R₄₇
R₄₈NCON (R₄₉) -Group, R₄₆A group having the same meaning as R,₄₆
COO-group, R₄₇OSO ₂-Group, cyano group or nitro
Groups. Where R₄₆Is an aliphatic group, an aromatic group,
Or represents a heterocyclic group, R₄₇, R₄₈And R₄₉Are each
Represents an aliphatic group, aromatic group, heterocyclic group or hydrogen atom.
You The meaning of aliphatic group, aromatic group or heterocyclic group was previously defined.
It has the same meaning as meant.

Next, preferred ranges of R _{51 to} R ₆₅ , k, d, e and f will be described.

R ₅₁ is preferably an aliphatic group or an aromatic group. R ₅₂ and R ₅₅ are preferably aromatic groups. R ₅₃ is preferably an aromatic group or a heterocyclic group.

In the general formula (Cp-3), R ₅₄ is R
_{A 41} CONH- group or an R ₄₁ R ₄₃ N- group is preferred. R
₅₆ and R ₅₇ are an aliphatic group, an aromatic group, R ₄₁ O-group, or R ₄₁ S- group, are preferred. R ₅₈ is preferably an aliphatic group or an aromatic group. In formula (Cp-6), R ₅₉ is preferably a chlor atom, an aliphatic group or an R ₄₁ CONH-group. d is preferably 1 or 2. R ₆₀ is preferably an aromatic group. In the general formula (Cp-7), R ₅₉ is R ₄₁ CON
H-groups are preferred. In the general formula (Cp-7), d
Is preferably 1. R ₆₁ is preferably an aliphatic group or an aromatic group. In general formula (Cp-8), e is preferably 0 or 1. R ₆₂ includes R ₄₁ OCONH- group, R ₄₁ C
The ONH- group or the R ₄₁ SO ₂ NH- group is preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring. In the general formula (Cp-9), R ₆₃ is R ₄₁ CONH-
Group, R ₄₁ SO ₂ NH— group, R ₄₁ R ₄₃ NSO ₂ — group, R ₄₁
SO ₂ - group, R ₄₁ R ₄₃ NCO- group, nitro group or cyano group is preferable, 1 is preferably 1 or 2. In the general formula (Cp-10), R ₆₃ is (R ₄₃ ) ₂ NCO-
A group, R ₄₃ OCO- group or R ₄₃ CO- group, and e
Is preferably 1 or 2. In the general formula (Cp-11), R ₅₄ is preferably an aliphatic group, an aromatic group or R ₄₁ CONH-group, and f is preferably 1. Further, A preferably has a diffusion resistant group.

In the general formula (I), preferred examples of L ₁ include the following.

(1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396, JP-A-60-
249148 and 60-249149, which are groups represented by the following general formula (T-1). Here, the * mark represents the position of bonding with A or L ₁ of the compound represented by the general formula (I), and the ** mark represents L ₁ or L _1.
Indicates the position to combine with ₂ .

[0034] Formula (T-1) * - ( W-CR 11 (R 12)) t - ** In formula, W is an oxygen atom, a sulfur atom or -NR ₁₃ - represents a group, R ₁₁ and R ₁₂ Represents a hydrogen atom or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2.
When t is 2, two -W-CR ₁₁ (R ₁₂ ) represent the same or different. When R ₁₁ and R ₁₂ represent a substituent, typical examples of the substituent and R ₁₃ include R ₁₅ group, R ₁₅ CO— group, R ₁₅ SO ₂ — group and R ₁₅ group.
Examples thereof include (R ₁₆ ) NCO-group and R ₁₅ (R ₁₆ ) NSO ₂ -group. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₁₆ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The case where each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and they are linked to form a cyclic structure is also included. Specific examples of the group represented by formula (T-1) include groups represented by the following chemical formulas 9 to 11.

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11] (2) Group that causes cleavage reaction by utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,292 can be mentioned. It can be represented by the following general formula (T-2).

General formula (T-2) * -Nu-Link-E-** In the formula, Nu represents a nucleophilic group, and an oxygen atom or a sulfur atom is an example of a nucleophilic species. E represents an electrophilic group and is a group capable of undergoing a nucleophilic attack from Nu to cleave the bond with the ** mark. Link represents a linking group that sterically relates Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by formula (T-2) are shown in Chemical formulas 12 to 13 below.

[0039]

[Chemical formula 12]

[0040]

[Chemical 13] (3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system, for example, US Pat. Nos. 4,409,323 and 4,42.
No. 1,845, JP-A Nos. 57-188035 and 58-
98728, 58-209736, 58-20.
No. 9738 is a group represented by the general formula (T-3) shown in Chemical formula 14 below.

[0041]

[Chemical 14] In the formula, *, **, W, R ₁₁ , R ₁₂ and t are (T
-1) has the same meaning as described above. However, R ₁₁ and R ₁₂ may bond to each other to form a benzene ring or a heterocyclic ring. Also, R ₁₁ or R ₁₂ and W
And may combine with each other to form a benzene ring or a heterocycle. Z ₁ and Z ₂ each independently represent a carbon atom or a nitrogen atom, and x and y represent 0 or 1. Z ₁
Is 1 when x is a carbon atom, and x is 0 when Z ₁ is a nitrogen atom. The relationship between Z ₂ and y is the same as the relationship between Z ₁ and x. Further, t represents 1 or 2, and t is 2
Then two [-Z ₁ (R ₁₁ ) _x = Z ₂ (R ₁₂ ) _y ]-
May be the same or different. Further, the —CH ₂ — group adjacent to the ** mark may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group.

Specific examples of (T-3) are shown below.
Shown in Chemical formula 18.

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

[0046]

[Chemical 18] (4) Group Utilizing Cleavage Reaction by Ester Hydrolysis For example, a linking group described in West German Laid-Open Patent No. 2,626,315, which has the following general formulas (T-4) and (T-
Examples include groups represented by 5). In the formula, * and **
The mark has the same meaning as described for the general formula (T-1).

General Formula (T-4) * -OCO-** General Formula (T-5) * -SCS-** (5) Group Utilizing Cleavage Reaction of Iminoketal For example, US Pat. No. 4,546,073. Which is a linking group represented by the general formula (T-6)
Is a group represented by.

[0048]

[Chemical 19] In the formula, * mark, ** mark and W have the same meanings as described in formula (T-1), and R ₁₄ has the same meaning as R ₁₃ . Specific examples of the group represented by formula (T-6) include groups represented by the following chemical formula 20.

[0049]

[Chemical 20] Preferred examples of L ₁ include general formulas (T-1) to (T-
5), particularly preferably (T-
1), (T-3) and (T-4). j is preferably 0 or 1.

In the general formula (I), the group represented by L ₂ represents a trivalent or higher-valent timing group, preferably the group represented by the following general formula (T-L ₁ ) or (T-L ₂ ). Is.

General formula (T-L ₁ ) *-W- [Z ₁ -R ₁₁ ) _x = Z ₂ (R ₁₂ ) _y ] _t -CH ₂ -** W, Z ₁ , Z ₂ in the formula, R ₁₁ , R ₁₂ , x, y and t
Represents the same meaning as described for the general formula (T-3). Further, * indicates A- (L ₁ ) _{1 in the} general formula (I).
The position at which it is bonded to − represents the position at which it is bonded to − (L ₃ ) _n -PUG. However, at least one of a plurality of R ₁₁ or R ₁₂ present is a substituted or unsubstituted methylene group, and represents a group bonded to — (L ₃ ) _n —PUG.

A preferred example of (T-L ₁ ) is when W represents a nitrogen atom, more preferably when W and Z ₂ are combined to form a 5-membered ring, and particularly preferably imidazole or This is the case of forming a pyrazole ring.

General formula (T-L ₂ ) *-N- (Z ₃ -**) _{2 In the} formula, * and ** are synonymous with general formula (T-L ₁ ). The Z ₃ group represents a substituted or unsubstituted methylene group, and the two Z ₃ groups may be the same or different. Further, two Z ₃ groups may combine to form a ring.

Specific examples of (T-L ₁ ) and (T-L ₂ ) are shown in the following chemical formulas 21 to 27, but the present invention is not limited thereto.

[0055]

[Chemical 21]

[0056]

[Chemical formula 22]

[0057]

[Chemical formula 23]

[0058]

[Chemical formula 24]

[0059]

[Chemical 25]

[0060]

[Chemical formula 26]

[0061]

[Chemical 27] However, the groups listed in the specific examples herein may further have a substituent, and examples of such a substituent include an alkyl group (for example, methyl, ethyl, isopropyl, t-butyl, hexyl, methoxymethyl). , Methoxyethyl, chloroethyl, cyanoethyl, nitroethyl, hydroxypropyl, carboxyethyl, dimethylaminoethyl, benzyl, phenethyl), aryl groups (eg phenyl,
Naphthyl, 4-hydroxyphenyl, 4-cyanophenyl, 4-nitrophenyl, 2-methoxyphenyl, 2,
6-dimethylphenyl, 4-carboxyphenyl, 4-
Sulfophenyl), a heterocyclic group (eg 2-pyridyl,
4-pyridyl, 2-furyl, 2-thienyl, 2-pyrrolyl), halogen atom (eg chloro, bromo), nitro group, alkoxy group (eg methoxy, ethoxy, isopropoxy), aryloxy group (eg phenoxy),
Alkylthio group (eg methylthio, isopropylthio, t-butylthio), arylthio group (eg phenylthio), amino group (eg amino, dimethylamino,
Diisopropylamino), acylamino group (eg acetylamino, benzoylamino), sulfonamide group (eg methanesulfonamide, benzenesulfonamide), cyano group, carboxyl group, alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl (Eg, phenoxycarbonyl) or a carbamoyl group (eg, N-ethylcarbamoyl, N-phenylcarbamoyl).

Of these, an alkyl group, a nitro group, an alkoxy group, an alkylthio group, an amino group, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, and a carbamoyl group are preferable.

In the general formula (T-L ₁ ), **
The —CH ₂ — group adjacent to the mark may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group.

In the general formula (I), m is preferably 1
Is.

In formula (I), the group represented by L ₃ has the same meaning as L ₁ .

In the general formula (I), n is preferably 0.
Alternatively, it is 1, and particularly preferably 0.

In the general formula (I), the photographically useful group represented by PUG is specifically a development inhibitor, a dye, a fogging agent, a developer, a coupler, a bleaching accelerator, a fixing accelerator and the like. Examples of preferable photographically useful groups are described in US Pat.
A photographically useful group described in 48,962 (in the patent,
Represented by the general formula PUG), JP-A-62-493.
The dyes described in 53 (wherein the leaving group part is released from the coupler), U.S. Pat. No. 4,477,56.
The development inhibitor described in JP-A No. 3-20, and JP-A-61-20
1247 and the bleaching accelerators described in JP-A-2-55 (the part of the leaving group released from the coupler in the specification). In the present invention, a development inhibitor is particularly preferable as the photographically useful group.

As the development inhibitor, the following chemical formula 2 is preferable.
General formulas (INH-1) to (INH shown in Chemical formulas 8 to 33)
It is a group represented by -13).

[0069]

[Chemical 28]

[0070]

[Chemical 29]

[0071]

[Chemical 30] R ₂₁ in the formula represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group (eg, methyl, ethyl, propyl, phenyl).

[0072]

[Chemical 31]

[0073]

[Chemical 32]

[0074]

[Chemical 33] In the formula, * represents a position at which the compound represented by the general formula (I) is bonded to the group represented by L ₂ or L ₃ .

Further, ** represents a position to be bonded to a substituent, and examples of the substituent include a substituted or unsubstituted aliphatic group, an aryl group and a heterocyclic group, which are present in the processing solution during photographic processing. It is preferable that the group decomposable by (4) is contained in these substituents.

Specifically, examples of the aliphatic group include methyl, ethyl, propyl, butyl, hexyl, decyl, isobutyl, t-butyl, 2-ethylhexyl, 2
-Methylthioethyl, benzyl, 4-methoxybenzyl, phenethyl, 1-methoxycarbonylethyl, propyloxycarbonylmethyl, methoxycarbonyl, phenoxycarbonyl, 2- (propyloxycarbonyl) ethyl, butyloxycarbonylmethyl, pentyloxycarbonylmethyl, 2 -Cyanoethyloxycarbonylmethyl, 2,2-dichloroethyloxycarbonylmethyl, 3-nitropropyloxycarbonylmethyl, 4-nitrobenzyloxycarbonylmethyl, 2,
5-dioxo-3,6-Jiokisadeshiru, -CO ₂ CH
A group represented by ₂ CO ₂ R ₁₀₀ may be mentioned.

Here, R ₁₀₀ represents an unsubstituted alkyl group having 1 to 8 carbon atoms. Further, examples of the aryl group include phenyl, naphthyl, 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 2-methylthiophenyl, 3-methoxycarbonylphenyl, 4-
(2-Cyanoethyloxycarbonyl) -phenyl may be mentioned.

Examples of the heterocyclic group include 4-pyridyl, 3-pyridyl, 2-pyridyl, 2-furyl and 2
-Tetrahydropyranyl.

Of these, INH is preferably (INH-1), (INH-2), (INH-3),
(INH-4), (INH-9) and (INH-1
2), and particularly preferably (INH-1) and (INH
-2) and (INH-3).

Further, as the substituent bonded to INH, an aliphatic group or a substituted or unsubstituted phenyl group is preferable.

Particularly preferred compounds represented by the general formula (I) are the following general formulas (Ia) and (Ib).
Is a compound represented by.

General formula (a) A- (L ₁ ) _j -W- [Z _1- (R ₁₁ ) _x = Z
_{2 (R 12) y] t} -CH 2 -PUG general formula _{(b) A- (L 1)} -N- (Z 3 -PUG) symbol ₂ wherein the general formula (I), (T-L ₁ ) and (T
-L ₂ ) It is synonymous with that explained above. In the general formula (Ia), j is preferably 0 or 1. In formulas (Ia) and (Ib), L ₁ is -OC (= 0)-.
A group is preferable, and a development inhibitor is preferable as PUG.

However, when a plurality of photographically useful groups have different functions, the timing group does not utilize intramolecular nucleophilic substitution.

The function of the photographically useful group means the function of the development inhibitor, dye, fogging agent, developer, coupler, bleaching accelerator or fixing agent.

Further, it is particularly preferable that the two or more PUGs released from the same compound are the same development inhibitor.

Next, the compound represented by formula (II) will be described. In the general formula (II), A and PUG have the same meaning as defined in the general formula (I). L ₄ is -OC
O- group, -OSO- group, -OSO ₂ - group, -OCS-
Group, -SCO- group, -SCS- group or -WCR ₁₁ R ₁₂
Represents a group. Here, W, R ₁₁ and R ₁₂ have the same meaning as defined in the general formula (T-1) in the description of L ₁ of the compound represented by the general formula (I).

A preferred example when L ₄ represents a --WCR ₁₁ R ₁₂ --group is when W represents an oxygen atom or a tertiary amino group, and more preferably L ₄ represents --OCH _2-.
A group or W and R ₁₁ or R ₁₂ represent a ring-forming group.

[0088] Further, L ₄ is -WCR ₁₁ R ₁₂ - may represent a group other than this L ₄ are preferably -OCO- group, -O
SO- group, -OSO ₂ - is a group, particularly preferably -O
It is a CO-group.

The group represented by L ₅ represents a group which releases PUG by electron transfer along the conjugated system or a group defined by L ₄ . The group that releases PUG by electron transfer along the conjugated system has the same meaning as the group represented by formula (T-3) in the description of L _{1 in} formula (I). L ₅ is preferably a group capable of releasing PUG by electron transfer along a conjugated system, and more preferably a group capable of binding to L ₄ at a nitrogen atom.

Among the compounds represented by the general formula (II), preferred are the compounds represented by the general formula (III) or general (IV) shown in the following chemical formulas 34 and 35.

General formula (III)

[0092]

[Chemical 34] In the formula, A has the same meaning as defined in formula (I). R ₁₀₁
And R ₁₀₂ each independently represent a hydrogen atom or a substituent. R ₁₀₃ and R ₁₀₄ each independently represent a hydrogen atom or a substituent. INH represents a group having a development inhibiting ability. R _{10 5} represents an unsubstituted phenyl group or a primary alkyl group, or a primary alkyl group substituted with a group other than an aryl group. However, at least one of R _{101 to} R ₁₀₄ is a substituent other than a hydrogen atom.

General formula (IV)

[0094]

[Chemical 35] The compound represented by the general formula (IV) will be described in detail. In the general formula (IV), A, INH, and R
₁₀₅ has the same meaning as defined in formula (III).
R ₁₁₁ , R ₁₁₂ and R ₁₁₃ each represent a hydrogen atom or an organic residue, and any two of R ₁₁₁ , R ₁₁₂ and R ₁₁₃ may be linked as a divalent group to form a ring.

The compound represented by formula (III) will be described in more detail.

In the general formula (III), A is the general formula (I).
Is synonymous with. R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or a substituent. Specific examples of the substituent include an aryl group (eg, phenyl, naphthyl, p-methoxyphenyl, p-hydroxyphenyl,
p-nitrophenyl, o-chlorophenyl), an alkyl group (for example, methyl, ethyl, isopropyl, propyl,
tert-butyl, tert-amyl, isobutyl, s
ec-butyl, octyl, methoxythymer, 1-methoxyethyl, 2-chloroethyl), halogen atom (eg fluoro, chloro, bromo, iodo), alkoxy group (eg methoxy, ethoxy, isopropyloxy, propyloxy, tert-butyloxy, isobutyl). Oxy, butyloxy, octyloxy, 2-methoxyethoxy, 2-chloroethoxy, nitromethyl, 2-cyanoethyl, 2-carbamoylethyl, or 2-dimethylcarbamoylethyl), an aryloxy group (eg, phenoxy, naphthoxy, or p-methoxyphenoxy). ), Alkylthio groups (eg methylthio, ethylthio, isopropylthio, propylthio, tert-butylthio, isobutylthio, sec-butylthio, octylthio or 2-methoxy). Ethylthio), arylthio groups (eg phenylthio, naphthylthio, or p-methoxyphenylthio), amino groups (eg amino, methylamino, phenylamino, dimethylamino, diethylamino, diisopropylamino, or phenylmethylamino), carbamoyl groups (eg carbamoyl). , Methylcarbamoyl, dimethylcarbamoyl, diethylcarbamoyl, diisopropylcarbamoyl, ethylcarbamoyl, isopropylcarbamoyl, tert-butylcarbamoyl, phenylcarbamoyl or phenylmethylcarbamoyl), sulfamoyl groups (eg sulfamoyl, methylsulfamoyl, ethylsulfamoyl, isopropylsulfamoyl) Famoyl, phenylsulfamoyl, octylsulfamoyl, dimethyl Rufamoyl, diethylsulfamoyl, diisopropylsulfamoyl, dihexylsulfamoyl, or phenylmethylsulfamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, tert-butyloxycarbonyl, tert-amyl) Oxycarbonyl, or octyloxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl or p-methoxyphenoxycarbonyl), an acylamino group (eg, acetylamino, propanoylamino, pentanoylamino, N-methylacetylamino, or benzoylamino) A sulfonamide group (for example, methanesulfonamide, ethanesulfonamide, pentanesulfonamide,
Benzenesulfonamide or p-toluenesulfonamide), an alkoxycarbonylamino group (for example, methoxycarbonylamino, isopropyloxycarbonylamino, tert-butoxycarbonylamino or hexyloxycarbonylamino), an aryloxycarbonylamino group (for example, phenoxycarbonylamino),
A ureido group (for example, 3-methylureido, or 3-phenylureido), a cyano group or a nitro group can be mentioned.

R ₁₀₁ and R ₁₀₂ may be the same or different, but the sum of the formula weights of both is preferably less than 120. Moreover, an alkyl group, a halogen atom, and an alkoxy group are mentioned as a preferable substituent, Especially preferably, it is an alkyl group.

In formula (III), the groups represented by R ₁₀₃ and R ₁₀₄ each independently represent a hydrogen atom or an alkyl group. Examples of the alkyl group include methyl,
Mention may be made of ethyl, isopropyl, tert-butyl, isobutyl, hexyl or 2-methoxyethyl. R ₁₀₃ and R ₁₀₄ are preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.

In formula (III), the group represented by R ₁₀₅ represents an unsubstituted phenyl group or a primary alkyl group, or a primary alkyl group substituted with a group other than an aryl group. Examples of the alkyl group include ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, 2
-Methylbutyl, hexyl, 2-methylpentyl, 3-
Methylpentyl, 4-methylpentyl, 2-ethylbutyl, heptyl, or octyl. Examples of the substituent include a halogen atom, an alkoxy group, an alkylthio group, an amino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group, an alkoxycarbonylamino group, a ureido group, a cyano group, a nitro group, or -CO ₂ CH ₂ CO
₂ A group represented by R ₁₀₆ can be mentioned, and specific examples of each group include those exemplified for the substituents of R ₁₀₁ and R ₁₀₂ , excluding the group containing an aryl group.

R ₁₀₆ represents an unsubstituted alkyl group having 3 to 6 carbon atoms (eg propyl, butyl, isobutyl, pentyl, isopentyl, hexyl).

Further, R ₁₀₅ may be substituted with two or more kinds of substituents. Preferred as the substituent of R ₁₀₅ is fluoro, chloro, alkoxy group, carbamoyl group, alkoxycarbonyl group, cyano group, nitro group or —CO ₂ CH ₂ CO ₂ R ₁₀₆ . Particularly preferred among these are an alkoxycarbonyl group, or -CO ₂ CH ₂ CO ₂ R ₁₀₆ groups.

Further, R ₁₀₅ is preferably a phenyl group, a primary unsubstituted alkyl group having 2 to 6 carbon atoms, or a primary alkyl group substituted by the groups mentioned above as the preferred substituents of R _105. is there. Particularly preferred is a primary unsubstituted alkyl group having 3 to 5 carbon atoms or a primary alkyl group substituted with an alkoxycarbonyl group.

In the general formula (III), the group represented by INH represents a group having a development inhibiting ability, and specific examples thereof include:
(INH-1) mentioned in the description of PUG of the general formula (I)
(INH-13). The preferable range and the like are also the same as in the case of the general formula (I).

Next, the compound represented by formula (IV) will be described in detail.

First, the case where each of R ₁₁₁ , R ₁₁₂ and R ₁₁₃ represents a hydrogen atom or a monovalent organic group will be described.

When R ₁₁₂ and R ₁₁₃ represent a monovalent organic group, the organic group is preferably an alkyl group (eg methyl, ethyl) or an aryl group (eg phenyl). R ₁₁₂ and R ₁₁₃ are preferred when at least one of them is a hydrogen atom, and particularly preferred when R ₁₁₂ and R ₁₁₃ are hydrogen atoms.

R ₁₁₁ represents an organic group, preferably the following groups. Alkyl groups (eg methyl, isopropyl, butyl, isobutyl, tert-butyl, se
c-butyl, neopentyl, hexyl), aryl groups (eg phenyl), acyl groups (eg acetyl, benzoyl), sulfonyl groups (eg methanesulfonyl, benzenesulfonyl), carbamoyl groups (eg ethylcarbamoyl, phenylcarbamoyl), sulfamoyl groups ( For example, ethylsulfamonol, phenylsulfamoyl), alkoxycarbaphonyl group (eg, ethoxycarbonyl, butoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl, 4-methylphenoxycarbonyl), alkoxysulfonyl group (eg, butoxysulfonyl). , Ethoxysulfonyl), an aryloxysulfonyl group (eg, phenoxysulfonyl,
4-methoxyphenoxysulfonyl), cyano group, nitro group, nitroso group, thioacyl group (eg thioacetyl, thiobenzoyl), thiocarbamoyl group (eg ethylthiocarbamoyl), imidoyl group (eg N-ethylimidoyl group), amino group (Eg amino, dimethylamino, methylamino), acylamino groups (eg formylamino, acetylamino, N-methylacetylamino), alkoxy groups (eg methoxy, isopropyloxy) or aryloxy groups (eg phenoxy).

Further, these groups may further have a substituent, and examples of the substituent include the groups mentioned as R ₁₁₁ , a halogen atom (eg fluoro, chloro, bromo), a carboxyl group, Examples thereof include a sulfo group.

R ₁₁₁ has 15 atoms other than hydrogen atoms.
The following is preferable.

Further, R ₁₁₁ is more preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted or unsubstituted alkyl group.

Next, in the groups represented by R ₁₁₁ , R ₁₁₂ and R ₁₁₃ , the case where any two of these groups are combined as a divalent group to form a ring will be described.

The size of the ring formed is preferably a 4- to 8-membered ring, more preferably a 4- to 6-membered ring.

Preferred as the divalent group are the following groups.

-C (= 0) -N (R ₁₁₄ )-, -SO _{2
-N (R 114) -, -} (CH 2) 3 -, - (CH 2) 4
_{-, - (CH 2) 5} -, - C (= 0) - (CH 2)
_2- , -C (= 0) -N ( _R114 ) -C (= 0)-,-
_{SO 2 -N (R 114) -C} (= 0) -, - C (= 0) -
_{C (R 114) (R 115} ) -, - (CH 2) 2 -O-CH
_2- .

Here, R ₁₁₄ and R ₁₁₅ are hydrogen atoms,
Alternatively, it has the same meaning as when R ₁₁₁ represents a monovalent organic group, and R ₁₁₄ and R ₁₁₅ may be the same or different.

Of R ₁₁₁ , R ₁₁₂ and R ₁₁₃ , the remaining groups not participating as a divalent group represent a hydrogen atom or a monovalent organic group, and specific examples of the organic group are shown when no ring is formed. The same as in the case of R ₁₁₁ , R ₁₁₂ , and R ₁₁₃ .

Any two of R ₁₁₁ , R ₁₁₂ , and R ₁₁₃
When two are joined to form a ring, preferably R ₁₁₂ and R
_{This is} the case where any one of ₁₁₃ is a hydrogen atom and the remaining R ₁₁₂ to R ₁₁₃ form a ring with R ₁₁₁ . More preferably, the left end of the divalent group mentioned above is bonded to the nitrogen atom of the general formula (I) and the right end thereof is bonded to the carbon atom.

Further, R ₁₁₁ , R ₁₁₂ and R ₁₁₃ are preferable when they do not form a ring and each represents a hydrogen atom or a monovalent organic group.

In the general formulas (I) and (II), the formula weight of the residue excluding the groups represented by A and PUG is preferably 64 or more and 240 or less, more preferably 7
It is 0 or more and 200 or less, and particularly preferably 90 or more and 180 or less.

Specific examples of the compounds represented by formulas (I) to (IV) of the present invention are shown in the following chemical formulas 36 to 70.
The present invention is not limited to these.

Regarding the compounds in which A represents a coupler residue in the general formula (I), the numbers prefixed with (CA) and those in the general formulas (II) to (IV) in which A represents a coupler residue are described. Is a number with (CB) attached to its head, and those of general formulas (I) to (IV) in which A represents a redox group are indicated with a number attached with (SA).

[0122]

[Chemical 36]

[0123]

[Chemical 37]

[0124]

[Chemical 38]

[0125]

[Chemical Formula 39]

[0126]

[Chemical 40]

[0127]

[Chemical 41]

[0128]

[Chemical 42]

[0129]

[Chemical 43]

[0130]

[Chemical 44]

[0131]

[Chemical 45]

[0132]

[Chemical 46]

[0133]

[Chemical 47]

[0134]

[Chemical 48]

[0135]

[Chemical 49]

[0136]

[Chemical 50]

[0137]

[Chemical 51]

[0138]

[Chemical 52]

[0139]

[Chemical 53]

[0140]

[Chemical 54]

[0141]

[Chemical 55]

[0142]

[Chemical 56]

[0143]

[Chemical 57]

[0144]

[Chemical 58]

[0145]

[Chemical 59]

[0146]

[Chemical 60]

[0147]

[Chemical formula 61]

[0148]

[Chemical formula 62]

[0149]

[Chemical 63]

[0150]

[Chemical 64]

[0151]

[Chemical 65]

[0152]

[Chemical 66]

[0153]

[Chemical 67]

[0154]

[Chemical 68]

[0155]

[Chemical 69]

[0156]

[Chemical 70] Synthesis of compounds of the present invention is described, for example, in US Pat.
No. 383, No. 4770990, No. 4684604,
U.S. Pat. No. 4,886,736, JP-A Nos. 60-218645, 61-230135, and Japanese Patent Application Nos. 2-37070 and 2;
The methods described in JP-A-170832 and JP-A-2-251192 or similar methods can be used.

A specific synthesis example will be described below.

(Synthesis Example 1): Exemplified Compound (CA-1)
Was synthesized by the synthetic route shown in the following Chemical Formula 71.

[0159]

[Chemical 71] CA-1a (3.40 g) was reacted in thionyl chloride (30 ml) at 60 ° C. for 1 hour, and then excess thionyl chloride was distilled off under reduced pressure. This residue was converted to CA-1b (7.48).
g) and diisopropylethylamine (10.5 ml) were added to a dimethylformamide solution (0 ° C.), and the mixture was stirred for 1 hour. Then, this solution was poured into water (500 ml), and the generated crystals were collected by filtration to obtain 9.8 g of CA-1c as crude crystals. The structure was confirmed by NMR.

CA-1c (3.20 g) and CA-1d
(1.38 g) and 1,2-dichloroethane (30 m
The reaction was carried out in l) for 1 hour. CA-1e (3.
A solution of 20 g) in ethyl acetate (20 ml) was added under water cooling,
Subsequently, diisopropylethylamine (4.5 ml) was added, followed by stirring for 1 hour.

The reaction was stopped with 1N hydrochloric acid, and chloroform (30 ml) was added to dilute the reaction solution. Then, the reaction solution was washed with water three times, and the organic layer was dried over sodium sulfate. The oily substance obtained by distilling off the organic solvent was subjected to silica gel column chromatography (ethyl acetate-hexane = 1: 1).
By purifying in 5), 1.20 g of Exemplified compound CA-1 was obtained. The structure was confirmed by NMR. m.
p. 133.0-134.0 ° C.

(Synthesis Example 2): Synthesis of Exemplified Compound (CA-19) It was synthesized by the synthetic route shown in the following Chemical Formula 72.

[0163]

[Chemical 72] CA-19a (10.7 g) and 37% formalin aqueous solution (30 ml) were reacted in acetic acid (100 ml) at 70 ° C. for 5 hours, and then the solvent was evaporated under reduced pressure. CA-19b was obtained by purifying the residue by silica gel column chromatography (ethyl acetate-hexane 2: 1).
Was obtained (6.4 g, yield 53%).

Next, CA-19b (3.2 g) and CA-
19c (2.1 g) was suspended in chloroform (40 ml), zinc iodide (5.7 g) was added thereto, and the mixture was reacted at room temperature for 2 hours. Stop the reaction with 1N hydrochloric acid and add chloroform 4
After diluting with 0 ml, the reaction solution was washed twice with water. The organic layer was dried over sodium sulfate and concentrated, and the obtained residue was purified by silica gel column chromatography (ethyl acetate-hexane 1: 4) to give 4.1 g of the exemplified compound (CA-19) (yield: 25%) was obtained. The structure was confirmed by NMR, mass spectrum and elemental analysis.

(Synthesis Example 3): Synthesis of Exemplified Compound (CA-2) It was synthesized by the synthetic route shown in Chemical Formula 73 below.

[0166]

[Chemical 73] CB-2a (10 mmol) was suspended in chloroform (30 ml), thionyl chloride (20 mmol) was added thereto, and 50
After reacting for 1 hour at ℃, the solvent was distilled off. The residue obtained here was mixed with CB-2b (10 mmol) and diisopropylethylamine (20 mmol) in dimethylformamide (3
0 ml) solution and reacted for 1 hour, then ice water (200 ml)
ml)). After adding 50 ml of chloroform and stirring, the aqueous phase was separated, and the organic phase was washed twice with water (100 ml). CB-2c was obtained by drying this organic layer with sodium sulfate and concentrating it.

The CB-2c thus obtained was mixed with chloroform (30
ml) and add nitrophenyl chlorocarbonate (10
mmol) was added and reacted for 1 hour. Then CB-2d
A solution of (10 mmol) in ethyl acetate (50 ml) was added, and further diisopropylethylamine (50 mmol) was added.
The reaction was carried out for 1 hour. The reaction was stopped by adding 1N hydrochloric acid (10 ml) and then diluted with ethyl acetate (10 ml). The organic layer was washed with water, dried over sodium sulfate and concentrated. The obtained residue was purified by silica gel column chromatography (eluent: ethyl acetate-hexane 1: 3) to give 1.94 g (23% yield) of Exemplified compound CB-2.
Got m. p. 101.5-102.5 ° C.

(Synthesis Example 4): Synthesis of Exemplified Compound CB-3 Synthesis was performed according to the synthetic route shown in Chemical Formula 74 below.

[0169]

[Chemical 74] Using (CB-3a) as a starting material, it was possible to synthesize by a method similar to that of Exemplified Compound CB-2. Yield 31%.
m. p. 68.0-69.0 ° C.

(Synthesis Example 5): Synthesis of Exemplified Compound (CB-16) Synthesis was performed according to the synthetic route shown in Chemical Formula 75 below.

[0171]

[Chemical 75] (CB-16a) 200 g and (CB-16b) 34.7
g was dissolved in ethyl acetate (500 ml), diisopropylethylamine (142 ml) was added thereto, and the mixture was stirred for 4 hours. The precipitated crystals were collected by filtration and washed with ethyl acetate to obtain 176 g (75%) of (CB-16c).

53.6 g of (CB-16c) and paraformaldehyde (27.9 g) were reacted in a mixture of 1,2-dichloroethane (500 ml) and acetic acid (54 ml) under reflux for 4 hours. .. After cooling to room temperature, the reaction solution was washed with water, dried over anhydrous sodium sulfate and concentrated. By purifying the obtained residue by silica gel column chromatography using chloroform as an eluent, (C
23.2 g (41.2%) of B-16d) was obtained.

(CB-16d) 23.2 g and (CB-1
6.78 g of 6e) was dissolved in chloroform (250 ml), 26.88 g of zinc iodide was added thereto, and the mixture was stirred for 3 hours. After adding 1N hydrochloric acid, the reaction solution was washed with water. The organic layer was dried over anhydrous sodium sulfate and concentrated, and the obtained residue was purified by silica gel column chromatography (ethyl acetate-hexane 1: 4) to give the exemplified compound (C
7.0 g of B-16) was obtained (23.9%). m. p. 1
17.0-118.5 ° C.

(Synthesis Example 6): Synthesis of Exemplified Compound (CB-18) Synthesis was carried out in the same manner as in Synthesis 5. m. p. 61.5
-63.0 ° C.

(Synthesis Example 7): Synthesis of Exemplified Compound CB-25 It was synthesized by the same method as Synthesis Example 2 of JP-A-60-218645. Yield 7% m. p. 115 ° C.

(Synthesis Example 8): Synthesis of Exemplified Compound SA-6 It was synthesized by the synthetic route shown in Chemical Formula 76 below.

[0177]

[Chemical 76] 11.6 g of SA-6a (synthesized by a method similar to that described in JP-A-61-230135) was added to thionyl chloride (30 ml) under water cooling, and the mixture was further reacted at 50 ° C. for 1 hour. Excess thionyl chloride was distilled off under reduced pressure, and the precipitated crystals were washed with a small amount of ice-cooled chloroform to give
SA-6b was obtained as crude crystals. Next, this SA-6b
13.1 g of N, N-dimethylformamide (10 g of SA-6c 7.2 g and triethylamine 12.1 g)
0 ml) solution was added at 0 ° C. and then further reacted at room temperature for 1 hour.

The reaction mixture was poured into an aqueous solution of 60 ml of 2N hydrochloric acid and 300 ml of ice water, and 300 ml of ethyl acetate was further added and stirred. The liquid was transferred to a separatory funnel, an oil layer was taken, and washed with water several times. The organic layer was dried over anhydrous sodium sulfate and concentrated, and then the residue was purified by silica gel column chromatography (ethyl acetate-hexane = 1/4 to 1/1 (V
/ V) was used as an eluent) to obtain 3.7 g of Exemplified Compound SA-6 as an amorphous substance.

The compounds represented by formulas (I) and (II) of the present invention may be added to any one layer in the light-sensitive material, but they may be added to the light-sensitive silver halide emulsion layer or its adjacent layer. It is preferably added, and particularly preferably added to the red or green photosensitive emulsion layer.

The total amount added to the light-sensitive material was 1.0 × 10.
^-4 was ^{g / m 2 ~0.8g / m 2} , preferably 1.
0 a ^{× 10 -3 g / m 2 ~0.5g} / m 2, more preferably ^{1.0 × 10 -2 g / m 2} ~0.3g / m 2.

In the present invention, the total dry film thickness is 22 μm or less, preferably 10 μm to 20 μm, more preferably 12 μm to 18 μm, particularly preferably 14 μm to
16 μm. From the viewpoint of sharpness and desilvering property, the thickness from the outermost surface of the light-sensitive material to the lower end of the light-sensitive silver halide emulsion layer closest to the support, which is closer to the support, is preferably 16 μm or less. To 14 μm from the surface to the outermost surface of the color-sensitive layer closest to the support.

Here, the dry total film thickness means a temperature of 25 ° C. and a humidity of 5
A commercially available contact-type film thickness meter (Anritsu Electric Co. Lt) under the condition of 5% humidity control for 2 days.
d. The value measured by K-402B STAND) is displayed. The total dry film thickness of all hydrophilic colloid layers on the side having the emulsion layer (that is, the total dry film thickness) is obtained after removing the thickness of the dried sample and the coating layer on the support on the side having the emulsion layer. It is obtained by the difference between the thickness and

The film thickness of each layer of the multilayer silver halide color light-sensitive material can be measured by enlarging and photographing the cross section using a scanning electron microscope. In the measurement of a scanning electron microscope, the sample usually has to be placed under a vacuum, and the condition of the humidity-controlled sample cannot be maintained. There is a case that there is a loss and the film thickness cannot be measured correctly. Therefore, the sample preparation method of the freeze-drying method has been tried, but it is not sufficient. The measurement by the cross-section photography of the scanning electron microscope is used as a measuring means for calculating the thickness of each layer of the dried sample based on the value of the film thickness by the contact-type film thickness meter.

The silver content of the light-sensitive material of the present invention is 1.0 g /
It is preferably m ² or more and 4.9 g / m ² or less,
More preferably 1.0 g / m ² or more and 4.7 g / m ² or less, and even more preferably 1.5 g / m ² or more and 4.5 g / m.
² or less, particularly preferably 2.0 g / m ² or more and 4.3 g /
m ² or less.

With the light-sensitive material having a low silver content as described above, sufficient sharpness and color reproducibility can be obtained because the coloring property is good, the molecular absorption coefficient of the coloring dye is large, and the long-wave tail of the hue is cut off. This is because the good coupler of the present invention was used and the dry film thickness was set to a thin place.

The term "content of silver" as used herein means the content of all silver such as silver halide and metallic silver converted into silver. Several methods are known for analyzing the content of silver in the light-sensitive material, and any method may be used. For example, the fluorescent X-ray method is convenient.

In the present invention, the specific photographic sensitivity defined below must be 80 or more and less than 800, but 10
It is more preferably 0 or more and 640 or less.

In the present invention, the specific photographic sensitivity as described in detail and defined below is adopted as the sensitivity of the photographic light-sensitive material for the following reason.

That is, ISO sensitivity, which is an international standard, is generally used as the sensitivity of a photographic light-sensitive material. With ISO sensitivity, the light-sensitive material is developed on the fifth day after exposure, and the development treatment is a process designated by each company. According to the present invention, the time until the development processing after exposure is shortened (0.
The specific photographic sensitivity as described below was adopted so that the sensitivity can be determined by a constant developing process for 5 to 6 hours).

The specific photographic sensitivity of the light-sensitive material in the present invention is determined according to the following test method according to ISO sensitivity. (According to JIS K 7614-1981, etc.) (1) Test conditions The test is conducted in a room at a temperature of 20 ± 5 ° C. and a relative humidity of 60 ± 10%, and the photosensitive material to be tested is left in this state for 1 hour or more. use. (2) Exposure (i) The relative spectral energy distribution of the reference light on the exposed surface is shown in Table A.

TABLE A Wavelength nm Relative Spectral Energy (1) 360 2 370 8 380 12 390 23 400 400 45 410 57 57 420 420 63 430 62 440 81 450 450 93 460 97 470 98 480 101 101 490 97 500 500 100 510 101 40 520 100 102 550 103 103 560 100 570 97 580 98 590 90 90 600 93 93 610 94 620 920 630 88 640 890 89 650 86 660 86 670 89 680 585 85 690 75 700 77 Note (1) The value of 560 nm was standardized to 100. is there.

(Ii) An illuminance change on the exposed surface uses an optical wedge, and in any part of the optical wedge used, the variation of the spectral transmission density is within 10% in the wavelength region of 360 to 700 nm, within 10% in the region of 400 nm or more, and in the region of 400 nm or more. Is used within 5%.

(Ii) The exposure time is 1/100 second.

(3) Development processing (i) From exposure to development processing, the photosensitive material to be tested is kept at a temperature of 20 ± 5 ° C. and a relative humidity of 60 ± 10%.

(Ii) The development treatment is completed within 30 minutes or more and 6 hours after exposure.

(Iii) The developing process is performed as follows.

1 color development 3 minutes 15 seconds, 38.0 ± 0.1 ° C. 2 bleaching 6 minutes 60 seconds, 38.0 ± 3.0 ° C. 3 water washing 3 minutes 15 seconds, 24 ± 4 ° C. 4 fixing 6 minutes 30 Second, 38.0 ± 3.0 ° C. 5 water washing 3 minutes 15 seconds, 24 ± 4 ° C. 6 stable 3 minutes 15 seconds, 38.0 ± 3.0 ° C. 7 drying 5 minutes or less The treatment liquid composition used in each step is as follows. Shown in. Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2 4 g 4- (N-ethyl-N-β-hydroxyethylamine) -2-methylaniline sulfate 4.5 g Water was added to 1.0 liter pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100. 0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water added 1.0 liter pH 6.0 Fixer ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate Aqueous solution (70%) 17 5.0 ml Sodium bisulfite 4.6 g Water was added to 1.0 liter pH 6.6 Stabilizing solution Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g 1.0 liter with addition of water (4) Concentration measurement Concentration is expressed by log ₁₀ (Φ ₀ / Φ). Φ ₀ is an illumination light flux for density measurement, and Φ is a transmitted light flux of the measured portion. The geometric condition for density measurement is that the illumination light flux is a parallel light flux in the normal direction,
The standard is to use the total luminous flux transmitted as the transmitted luminous flux and diffused in the half space, and when other measuring methods are used, the correction is performed by the standard density piece. In addition, the emulsion film surface shall face the light receiving device side during measurement. Density measurement is performed with blue, green, and red status M densities, and its spectral characteristics are those shown in Table 1 as the overall characteristics of the light source, optical system, optical filter, and light receiving device used in the densitometer.

[0198]

[Table 1] (5) Determination of specific photographic sensitivity Using the results of processing and density measurement under the conditions shown in (1) to (4), the specific photographic sensitivity is determined by the following procedure.

(I) The exposure amounts corresponding to the densities higher by 0.15 with respect to the minimum densities of blue, green and red are expressed in lux-seconds and are respectively H _B , H _G and H _R.

(Ii) The larger value (lower sensitivity) of H _B and H _R is designated as H _S.

(Iii) The specific photographic sensitivity S is calculated according to the following formula 1.

[0202]

[Equation 1] The photographic material of the present invention has a specific photographic sensitivity of 80 or more and less than 800 determined by the above method. If it is less than 80, the aperture will open during normal shooting, and the out-of-focus probability, the probability of camera shake due to a slow shutter speed, the probability of underexposure increase, and the failure rate increases. In addition, many recent cameras have an automatic sensitivity setting function by reading a DX code, but among them, inexpensive cameras called so-called compact cameras often have a sensitivity setting of less than ISO100 and cannot be set as ISO sensitivity display of 100. that's all,
This camera cannot be applied to these cameras unless the specific sensitivity is at least 80 or more. Further, when the specific photographic sensitivity is set to 800 or more as disclosed in JP-A-63-22651, deterioration in graininess is conspicuous especially when the magnification is increased, which is not preferable.

The light-sensitive material of the present invention has at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and blue-sensitive silver halide emulsion layer, but any emulsion layer having the same color-sensitivity. Is preferably composed of two or more emulsion layers having different sensitivities, and more preferably a method of further improving the graininess in a three-layer structure. These techniques are described in British Patent No. 923,045 and Japanese Patent Publication No. 49-154, respectively.
No. 95.

In a color negative photographic light-sensitive material, when an emulsion layer having the same color sensitivity is composed of two or more emulsion layers having different sensitivities, the so-called grain disappearing effect is utilized so that the silver of the emulsion layer having a higher sensitivity can be used. It was common knowledge to design a high content of color negative photographic light-sensitive material. However, in a high-speed color negative photographic light-sensitive material having a specific photographic speed of 80 or more and less than 800, increasing the content of silver in the emulsion layer having a higher sensitivity is more effective than increasing the content of silver in the emulsion layer having a low sensitivity. It was found that there was an unexpected result that the deterioration with time was large. Therefore, it is preferable not to increase the silver content in the emulsion layer having the highest sensitivity among the emulsion layers having the same color sensitivity. The silver content of the most sensitive emulsion layer of each of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer is preferably 0.3 g / m ² or more and 1.5.
g / m ² or less, more preferably 0.3 g / m ² or more
It is 2 g / m ² or less, more preferably 0.3 g / m ² or more and 1.0 g / m ² or less.

Various inventions concerning the order of layer arrangement have been made in order to achieve both high sensitivity and high image. These techniques may be used in combination. Inventions relating to the order of layer arrangements are described, for example, in US Pat. No. 4,184,876.
No. 4,129,446, 4,186,016
No., UK 1,560,965, US Pat. No. 4,18
6,011, 4,267,264, 4,17
3,479, 4,157,917, 4,16
5,236, British Patent No. 2,138,962, JP-A-59-177552, British Patent No. 2,137,37.
No. 2, JP-A-59-180556 and JP-A-59-2040.
No. 38 and the like.

Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity.

A sensitivity layer may be improved by providing a reflection layer of fine grain silver halide under the high sensitivity layer, particularly the high sensitivity blue sensitive layer. This technique is described in JP-A-59-160135.

It is general that the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler. You can also For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure.

Further, as described in US Pat. No. 3,497,350 or JP-A-59-214853, the color sensitivity of the emulsion layer and the color image-forming coupler are appropriately combined, and this layer is removed from the support. A method of providing the furthest position can also be used.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride can be used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention. Good.
A preferred silver halide is silver iodobromide containing 30 mol% or less of silver iodide. 2 to 20 mol% preferred
Silver iodobromide including silver iodide.

In the present invention, in order to achieve high image quality at a low silver content, it is particularly preferable that the silver halide content of all emulsion layers be 5.6 mol% or more.

In the present invention, the average silver iodide content of silver halide in all emulsion layers means the total amount of iodine based on the total amount of silver halide (excluding metallic silver) present in the light-sensitive material. It is a value obtained by multiplying by 100 excluding. In the present invention, the average silver iodide content is preferably 5.6 mol% or more,
The content is more preferably 6.0 mol% or more and 15 mol% or less, and further preferably 7.0 mol% or more and 12 mol% or less.

It is known that if the average silver iodide content of silver halide is increased, graininess is improved, but on the contrary, there are drawbacks such as a slow developing speed, desilvering and a slow fixing speed. (For example, as described in JP-A-62-89963). However, the present inventor found that the total dry film thickness of the light-sensitive material and the amount of silver contained were reduced as in the present invention, and the sensitivity was specified, and that the use of the coupler of the present invention did not cause these problems. It was

The light-sensitive material of the present invention can be used in the color development processing step of performing color development processing containing an aromatic primary amine developing agent, desilvering processing, followed by washing and / or stabilization processing. It is particularly preferable that the processing time is 150 seconds or less in order to shorten the total development processing steps. Conventional light-sensitive materials have problems such as a reduction in color density and a decrease in color reproducibility when the time of color development step is shortened, but these drawbacks are caused by using the coupler of the present invention and reducing the total dry film thickness. I was able to solve it by setting it.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferable example is a p-ferrenine diamine derivative, and representative examples thereof are shown below, but the present invention is not limited thereto.

D-1 N, N-diethyl-p-ferreninediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- [N-ethyl-N-laurylamino) toluene D- 4 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino -3-Methyl-N-ethyl-N-
[Β- (Methanesulfonamide) ethyl] aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-ferreninediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Of the above p-ferrenine diamine derivatives, Exemplified Compound D-5 is particularly preferable.

Further, these p-ferrenine diamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates.

The above color developing agent is color developing solution 1
It is used in the range of 0.013 mol to 0.065 mol per liter, but 0.016 mol to 0.06 mol from the viewpoint of speeding up.
48 mol is preferable, and especially 0.019 mol to 0.03
2 mol is preferred.

In the color developing solution, as a preservative, sodium sulfite, potassium sulfite, sodium bisulfite,
Sulfite salts such as potassium bisulfite, sodium metasulfite and potassium metasulfite, and carbonyl sulfite adducts can be added as necessary.

The preferred amount of the preservative is the color developer 1
0.5-10 g per liter, more preferably 1-5
It is g.

Further, various hydroxylamines (for example, JP-A Nos. 63-5341 and 63-63) are used as compounds for directly preserving the aromatic primary amine color developing agent.
The compounds described in No. 106655, especially the compounds having a sulfo group or a carboxy group are preferable. ), JP-A-63-
Hydroxamic acids described in No. 43138, 63-146.
No. 041 hydrazines and hydrazides, 63-
44657 and 63-58443, α-hydroxyketones and α-aminoketones and 63-362 and 63-362.
It is preferable to add various sugars described in No. 44. Also,
In combination with the above compound, JP-A Nos. 63-4235 and 6-6.
No. 3-24254, No. 63-21647, No. 63-1
46040, 63-27341 and 63-25.
No. 654, etc., monoamines, 63-30845.
Nos. 63-14640, 63-43139, and the like, diamines, 63-21647, and 63-2.
6655 and 63-46655, polyamines described in 63-53551, nitroxy radicals described in 63-53551, alcohols described in 63-43140 and 63-53549, oximes described in 63-56654. And the tertiary amines described in JP-A-63-239447 are preferably used.

Other preservatives are described in JP-A-57-441.
Various metals described in No. 48 and No. 57-53749,
Salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3582, polyethyleneimines described in JP-A-56-94349, and aroma described in US Pat. No. 3,746,544. A group polyhydroxy compound or the like may be contained if necessary. It is particularly preferable to add an aromatic polyhydroxy compound.

In the present invention, the pH of the color developing solution is 9.
It is set in the range of 5-12, but from the point of speeding up, 1
It is preferably 0.2 or more, and particularly preferably 10.5 to 11.5.

By increasing the pH, it is possible to accelerate both the silver development and the color development reaction, and it is particularly effective in accelerating the color development of the cyan dye.

In order to raise the pH, it is preferable to increase the addition amount of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide and to increase the amount of an alkali buffering agent such as potassium carbonate or trisodium phosphate. The amount of such a buffering agent is 0.2 mol to 1.0 per liter of the developing solution.
Mol, preferably 0.3 mol to 0.8 mol, and particularly preferably 0.35 mol to 0.5 mol.

The developing step may be carried out in two or more baths having different pHs. For example, the first bath is treated with a developer having a pH of 9 or less for a very short time, and then a high pH of 10.5 or more is developed. By processing with the liquid, the development progress balance of the upper layer and the lower layer can be adjusted.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of the buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, potassium phosphate diphosphate, sodium borate and borophosphate. Potassium salt, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (5-sulfosalicylic acid) Sodium), 5-sulfo-2
-Potassium hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffering agent added to the color developing solution is 0.1.
It is preferably at least mol / liter, particularly 0.1
It is particularly preferable that the amount is ˜0.4 mol / liter.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids. Typical examples of these are nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N,
N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1, 2,4-
Tricarboxylic acid, 1-hydroxyethylidene-1,1-
Examples thereof include diphosphonic acid and N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid. Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution,
For example, it is about 0.1 g to 10 g per liter.

A bromide of 0.02 mol / liter or less is added to the color developing solution for the purpose of adjusting a fog inhibitor and adjusting gradation, but preferably 0.015 mol / l for rapid development. It is preferably less than or equal to liter.
As the above bromide, alkali metal bromides such as potassium bromide, sodium bromide, lithium bromide and the like can be preferably used.

Various antifoggants can be used in order to suppress fog and improve discrimination. Preferred examples of the antifoggants include benzotriazole, 5-methylbenzotriazole, 6-nitrobenzimidazole, 5-phenyltetrazole, 1-phenyl-5-mercaptotetrazole and the like. F. A. Mason, Photographic Processing Chemistry, Second Edition (published in 1675),
The organic antifoggants described on pages 39 to 42 can be mentioned, and the amount thereof is preferably the amount described in the same publication.

In addition, T. H. 4-Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and the like described in James, The Theory of Photographic Process, Fourth Edition, pages 398 to 399 are also preferable, and the amount thereof is also used. Is the same as the above organic antifoggant.

In order to accelerate the development, it is also preferable to use various development accelerators in the color developing solution. Examples of these development accelerators include L. F. A. Mason's book 41
The compounds described on pages 14 to 44 and various black-and-white developing agents described on pages 15 to 29 of the same book can be used in combination, and among them, pyrazolidones such as 1-phenyl-3-pyrazolidone and p-aminophenol are particularly preferable. And tetramethyl-p-phenylenediamine.

The preferred amount of these development accelerators used is
0.001 g to 0.1 g per liter of developer,
Particularly preferably, it is 0.003 g to 0.05 g.

The color developer used in the present invention may contain a fluorescent whitening agent. As optical brighteners, 4,
A 4'-diamino-2,2'-disulfostilbene compound is preferred. The addition amount is 0 to 5 g / liter, preferably 0.1 g to 4 g / liter.

If necessary, an alkyl sulfonic acid,
You may add various surface active agents, such as an aryl sulfonic acid, a fatty acid kalibonic acid, and an aromatic carboxylic acid.

The processing temperature in the color developing solution in the present invention is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds, and more preferably 1 minute to 2 minutes and 30 seconds.

The present invention is preferably carried out with a color development time of 150 seconds or less. Here, the development time is the time from the first dipping of the photosensitive material in the color developing solution to the first dipping in the processing solution of the next step, and includes the aerial time for moving between steps. To do.

Generally, the air time is 1 to 30 seconds,
For the purpose of speeding up the present invention, it is preferable that the air time is short, specifically 15 seconds or less, particularly 10 seconds or less.

The effect of the present invention is remarkable in the treatment for a shorter time. From this point, it is more preferably 120 seconds or less, and most preferably 100 seconds or less.

If necessary, the color developing bath may be divided into two or more baths, and the color developing replenisher may be replenished from the frontmost bath or the last bath to shorten the developing time or reduce the replenishing amount. ..

The processing method of the present invention can also be used for color reversal processing. The black-and-white developing solution used at this time is called a black-and-white first developing solution which is generally used for reversal processing of color light-sensitive materials, and it is used for black-and-white silver halide light-sensitive material processing solutions. Various well-known additives that are used by being added to the liquid can be contained.

A typical additive is 1-phenyl-
3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfite, accelerators composed of alkali such as sodium hydroxide, sodium carbonate and potassium carbonate, potassium bromide and 2-methylbenzimidazole, methyl Examples thereof include inorganic or organic inhibitors such as benzothiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds.

When processing with the above-mentioned developing solution in an automatic developing machine, it is preferable that the area where the developing solution comes into contact with air (opening area) is as small as possible. For example, opening area (c
When the aperture ratio is the value obtained by dividing m ² ) by the volume (cm ³ ) of the developer, the aperture ratio is preferably 0.01 or less, more preferably 0.005 or less.

Further, in order to correct the concentration of the developing solution due to evaporation, it is preferable to add water corresponding to the amount of evaporation.

The present invention is also effective when the developer is regenerated and used.

The color developing solution in the present invention is preferably used continuously by supplying a replenishing solution. The replenisher contains an amount necessary for compensating for components that have been consumed in development or consumed with time. Therefore, it usually contains a slightly larger amount of components than the developing mother liquor. The ratio is generally 10 to 50% larger than that of the mother liquor.

However, since bromide is eluted from the light-sensitive material with development, the content of the replenishing solution is preferably set smaller than that of the mother liquor, and it is more preferable to reduce the replenishing rate. For example, when the replenishing amount per 1 m ^{2 of} the light-sensitive material is set to 700 ml or less, the bromide content is preferably 0.004 mol or less per liter, and when the replenishing amount is 500 ml or less, 0.03 mol or less.
It is preferable that the amount is less than or equal to mol. Further, when the replenishment amount is reduced, it is also preferable not to include bromide.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment may be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III), such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are used from the viewpoint of rapid treatment and prevention of environmental pollution. preferable. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution.
The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, Kaisho 53-32736, 53-57831, 5
No. 3-37418, No. 53-72623, No. 53-9
No. 5630, No. 53-95631, No. 53-1042
No. 32, No. 53-124424, No. 53-14162
No. 3, No. 53-28426, Research Disclosure No. 17129 (July 1978), etc., a compound having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832.
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748.
Polyoxyethylene compounds described in JP-A No. 430; polyamine compounds described in JP-B-45-8836; other JP-A-49-40943, 49-59644, 53
-94927, 54-35727, 55-26.
Compounds described in Nos. 506 and 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-9563.
The compounds described in No. 0 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (p
Ka) is a compound of 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Use of thiosulfates is preferred. It is common and in particular ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent No. 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment.
Preferably, imidazole, 1-methylimidazole,
It is preferable to add 0.1 to 10 mol / liter of imidazoles such as 1-ethylimidazole and 2-methylimidazole.

The total time for the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved,
In addition, the occurrence of stains after the treatment is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-6-62 is disclosed.
No. 183,461, a method of improving the stirring effect by using a rotating means, and further stirring by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to make the emulsion surface turbulent. There are a method of improving the effect and a method of increasing the circulation flow rate of the entire processing liquid. Such a stirring effect improving means is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring effect accelerates the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering rate. Further, the above-mentioned stirring effect improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator.

Automatic developing machines used for processing the light-sensitive material of the present invention are disclosed in JP-A-60-191257 and 60-19.
It is preferable to have a means for transporting the light-sensitive material described in Nos. 1258 and 60-191259. As described in JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as couplers), the application, and the temperature of the rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows.
tty of Motion Picture
64 Television Engineers
Vol. 248 to 253 (May 1955 issue).

According to the multistage countercurrent method described in the above document,
Although the amount of washing water can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and adhered floating substances to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be very effectively used. In addition, JP-A-57
No.-8542, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing Co., Ltd. , Sanitary Engineering Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982)
It is also possible to use the bactericides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society (1986).

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but are generally in the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

In addition, there is a case where the washing treatment is further followed by a stabilizing treatment. As an example thereof, a stabilizing agent containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure 14850 and No. 15159, aldol compounds described in No. 13,924, US Pat. Metal salt complexes described in Japanese Patent No.
The urethane type compound of 3-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are, for example, JP-A Nos. 56-64339 and 57-57.
-144547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

The silver halide light-sensitive material of the present invention is described in, for example, US Pat. No. 4,500,626 and JP-A-60-1.
No. 33449, No. 59-218443, No. 61-23.
It can also be applied to the photothermographic materials described in No. 8056 and European Patent 210.660A2.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18716.
(November 1979), p.648, ibid. 307105
(November 1989), pages 863-865, and "Graphics and Chemistry of Photography" by Graphide, published by P. Glafkides, Chemie et Ph.
isique Photographie, Pau
L Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating P
photographic Emulsion, Foca
l Press, 1964) and the like.

For example, US Pat. No. 3,574,628,
No. 3,655,394 and British Patent No. 1,413,
Monodisperse emulsions described in, for example, No. 748 are also preferable.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. The tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photogr), for example.
apic Science and Engineer
ing), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
No. 4,310, No. 4,433,048, No. 4,4
It can be easily prepared by the method described in 39,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions in the inside and the outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed, or a type having a latent image on both the surface and the inside. It must be a negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. This core /
A method for preparing a shell type internal latent image type emulsion is described in JP-A-59-1
No. 33542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, ibid. 18716 and the same No. Three
07105, and the relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having different characteristics of at least one of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. What is a silver halide emulsion whose inside or surface is fogged?
It refers to a silver halide emulsion that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but is 0.01 to 0.75 as an average grain size.
μm, particularly 0.05 to 0.6 μm is preferable. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or number of silver halide grains are ± 40 of the average grain size). %) Is preferable.

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is 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, if necessary. Preferably silver iodide is 0.
The content is 5 to 10 mol%.

The fine grain silver halide preferably has an average grain diameter (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 2 μm.

Fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains.

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

[0284]Type of additive RD17643 RD18716 RD307105  [December 1978] [November 1979] [November 1989] 1 Chemical sensitizer page 23 648 page right column 866 page 2 sensitivity enhancer page 648 right column 3 spectral sensitizer, pages 23-24 648 Page right column to 866 to 868 page Supersensitizer 649 page right column 4 Whitening agent page 24 647 page right column 866 page 5 Fog inhibitor, page 24 to 25 page 649 right column 868 to 870 page stabilizer 6 Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7 stain inhibitor page 25, right column, page 650, left column to page 872, right column 8 dye image stabilizer page 25, 650 Page left column 872 Page 9 Hardener 26 page 651 Page left column 874 to 875 page 10 Binder page 26 651 Page left column 873 to 874 page 11 Plasticizer and lubricant page 27 650 page right column 876 page 12 Coating aid, Page 26-27 Page 650 Right column 875-876 Page Surfactant 13 Static 27 page 650 Page right column 876-877 Page 514 Anti-blocking agent 14 Matting agent Page 878-879 Also prevent deterioration of photographic performance due to formaldehyde gas.
In order to stop, U.S. Pat.
Formaldehyde described in 4,435,503
A compound that can be reacted and immobilized can be added to the light-sensitive material.
And are preferred.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Application Laid-Open No. 1-1060.
It is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, as described in No. 52, regardless of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention has the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-2593
It is preferable to include the dye described in No. 58.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure (RD) No. 17643, VII-CG, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
1,432, 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A Nos. 60-43659, 61-72238, and 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, and 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
No. 4,775,616, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199, JP-A-61-42658 and the like are preferable. Further, JP-A 64-553 and 64-5.
54, 64-555 and 64-556, and pyrazoloazole couplers described in US Pat. No. 4,811.
The imidazole couplers described in No. 8,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A.
No.

As couplers in which the color forming dye has an appropriate diffusibility, US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No.
17643, Item VII-G, ibid. VII of 307105-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, section VII-F and ibid. 307105, VII-
Patents described in paragraph F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, there is described in British Patent 2,093.
7,140, 2,131,188, JP-A-59-
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DIR described in JP-A-62-24252
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 1
Nos. 73,302A and 313,308A, RD No., a coupler which releases a dye that recovers color after separation. 114
49, ibid. No. 24241, bleach accelerator releasing couplers described in JP-A No. 61-201247, US Pat.
55,477 and the like, a coupler releasing a leuco dye described in JP-A-63-75747, and a coupler releasing a fluorescent dye described in U.S. Pat. No. 4,774,181. .

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric 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-2-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or Esters of phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl 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.), amides (N, N-diethyl ester) Dodecanamide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.),
Alcohols or phenols (isostearyl alcohol, 2,4-di-t-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate) , Trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-t octylaniline, etc.),
Hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like can be mentioned. 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. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-25747 and JP-A-62-2.
No. 72248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid. 18
716, page 647, right column to page 648, left column, and RD. Three
07105, page 897.

The film swelling speed T _1/2 of the light-sensitive material of the present invention is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Photographic Sanence and Engineering (Photogr. Sci Eng.), Vol. 19, 2 by A. Green et al.
No., pages 124 to 129, and can be measured by using a swellometer (swelling meter) of the type described above. T _1/2 is the maximum swell reached when the color developer is processed at 30 ° C. for 3 minutes and 15 seconds. 90% of the film thickness is defined as the saturated film thickness, which is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

[0308]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared. The amount coated amount (Composition of photosensitive layer) is expressed in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown by the number of moles per mole of silver halide in the same layer. First layer (antihalation layer) Black colloidal silver 0.25 Gelatin 1.30 ExM-1 5.0 × 10 ^-3 Second layer (intermediate layer) Gelatin 1.50 UV-1 3.0 × 10 ^-2 UV -2 6.0 x 10 ^-2 UV-3 7.0 x 10 ^-2 ExF-1 4.0 x 10 ^-3 Solv-2 7.0 x 10 ^-2 Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 29%, normal crystal, twin crystal mixed grains, diameter / thickness ratio 2.5) Silver coating Amount 0.45 Gelatin 1.50 ExS-1 1.0 × 10 ⁻⁴ ExS-2 3.0 × 10 ⁻⁴ ExS-3 1.0 × 10 ⁻⁵ ExC-1 0.11 ExC-3 0.11 ExC-4 3.0 × 10 ^-2 ExC-7 1.0 × 10 ^-2 Compound of the present invention (CB-18) 1.0 × 10 ^-2 Solv-1 7.0 × 10 ^-3 4th layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 14 mol%, internal high AgI type, equivalent sphere diameter 0.5 μm, variation coefficient of equivalent sphere diameter 20%, normal crystal, twin Crystal mixed particles, diameter / thickness ratio 1.0) Silver coating amount 0.55 Gelatin 1.50 ExS-1 1.0x10 ^-4 ExS-2 3.0x10 ^-4 ExS-3 1.0x10 ^-5 ExC-1 0.16 ExC-2 8.0 x 10 ^-2 ExC-3 0.17 ExC-7 1.5 x 10 ^-2 Compound of the present invention (CB-18) 2.5 x 10 ^-2 ExY-2 1.0 × 10 ^-2 Cpd-10 1.0 × 10 ^-4 Solv-1 0.10 Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 8 mol%, internal height) AgI type, equivalent sphere diameter 0.50 μm, variation coefficient of equivalent sphere diameter 17%, twin mixed particles, diameter / thickness ratio 6.5) Silver coating amount 0.55 Gelatin 1 ^{60 ExS-1 1.0 × 10 -4} ExS-2 3.0 × 10 -4 ExS-3 1.0 × 10 -5 ExC-5 7.0 × 10 -2 The compounds of the invention (CB-18) 2.0 x 10 ^-2 ExC-6 8.0 x 10 ^-2 ExC-7 1.5 x 10 ^-2 Solv-1 0.15 Solv-2 8.0 x 10 ^-2 6th layer (intermediate layer) Gelatin 1.30 P-2 0.17 Cpd-1 0.10 Cpd-4 0.17 Solv-1 5.0 × 10 ^-2 7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, sphere equivalent diameter 0.25 μm, variation coefficient of sphere equivalent diameter 17%, tetrahedral grain) Silver coating amount 0.30 Gelatin 0.80 ExS-4 5.0 × 10 ^-4 ExS ^{-5 2.0 × 10 -4 ExS-6} 0.3 × 10 -4 ExM-1 3.0 × 10 -2 ExM-2 0.20 the compounds of the invention (CB ^{18) 1.0 × 10 -2 Cpd-} 11 7.0 × 10 -3 Solv-1 0.20 Eighth Layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI Type, sphere equivalent diameter 0.45 μm, variation coefficient of sphere equivalent diameter 20%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 4.0) Silver coating amount 0.50 Gelatin 1.10 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 3.0 × 10 ^-5 ExM-1 3.0 × 10 ^-2 ExM-2 0.25 ExM-3 1.5 × 10 ^-2 Compound (CB-18) of the present invention 2.0 × 10 ⁻² Cpd-11 9.0 × 10 ⁻³ Solv-1 0.20 9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 7 mol%, internal high AgI type, sphere equivalent diameter 0.60 μm, variation coefficient of sphere equivalent diameter 18%, normal crystal, twin mixed particles, diameter / thickness ratio 5.0) Silver Coating amount 0.45 Gelatin 1.00 ExS-4 2.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 2.0 × 10 ^-5 ExS-7 3.0 × 10 ^-2 ExM −1 1.0 × 10 ⁻² ExM-4 3.9 × 10 ⁻² ExM-5 2.6 × 10 ⁻² Compound of the present invention (CB-18) 3.0 × 10 ⁻² Cpd-2 1. 0x10 ^-2 Cpd-9 2.0x10 ^-4 Cpd-10 2.0x10 ^-4 Solv-1 0.20 Solv-2 5.0x10 ^-2 10th layer (yellow filter layer) Gelatin 0.90 Yellow colloid 5.0 × 10 ^-2 Cpd-1 0.20 Solv-1 0.15 11th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type) , Sphere equivalent diameter 0.5 μm, variation coefficient of sphere equivalent diameter 15%, octahedral grain) Silver coating amount 0.40 Gelatin 1.20 ExS-8 2.0 × 10 ⁻⁴ ExY-1 9.0 × 10 ⁻² ExY-3 0.90 Cpd-2 1.0 × 10 ⁻² Solv-1 0.30 12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 0.90 μm, variation coefficient of sphere equivalent diameter 15%, normal crystal, twin crystal mixed grains, diameter / thickness ratio 5.5) Silver coating Quantity 0.45 Gelatin 0.60 ExS-8 1.0x10 ^-4 ExY-3 0.12 Cpd-2 1.0x10 ^-3 Solv-1 4.0x10 ^-2 13th layer (1st layer Protective Layer) Fine grain silver iodobromide (average particle size 0.07 μm, AgI 1 mol%) 0.15 gelatin 0.80 UV-2 0.10 UV-3 0.10 UV-4 0.20 Solv-34 0.0 × 10 ^-2 P-2 9.0 × 10 ^-2 14th layer (second protective layer) Gelatin 0.70 B-1 (diameter 1.5 μm) 0.10 B-2 (diameter 1.5 μm) 0.10 B-3 2.0 × 10 ^-2 H-1 0.40 Furthermore, storability, processability, pressure resistance, mildew / bacterial resistance, electrostatic charge In order to improve the prevention property and coating property, the following Cpd
-3, Cpd-5, Cpd-6, Cpd-7, Cpd-
8, P-1, W-1, W-2, W-3 were added. In addition to the above, n-butyl-p-hydroxybenzoate was added. Furthermore, B-4, F-1, F-4, F-5, F
-6, F-7, F-8, F-9, F-10, F-11 and iron salts, lead salts, gold salts, platinum salts, iridium salts and rhodium salts are contained.

The chemical structural formulas or names of the compounds used in the present invention are shown in Chemical Formulas 77 to 89 below.

[0310]

[Chemical 77]

[0311]

[Chemical 78]

[0312]

[Chemical 79]

[0313]

[Chemical 80]

[0314]

[Chemical 81]

[0315]

[Chemical formula 82]

[0316]

[Chemical 83]

[0317]

[Chemical 84]

[0318]

[Chemical 85]

[0319]

[Chemical formula 86]

[0320]

[Chemical 87]

[0321]

[Chemical 88]

[0322]

[Chemical 89] Sample 101 had a total dry film thickness of 16.3 μm and a silver content of 4.1 g / m ² . (Samples 102 to 104) Samples 102 and 103 were prepared by increasing the amount of gelatin in each layer of Sample 101 by 16%, 42% and 55%.
And 104 were made. (Samples 105 to 108) Third layer of Samples 101 to 104,
Samples 105 to 108 were prepared by substituting the compound (CB-18) of the present invention for the fourth layer, the eighth layer, the ninth layer and the eleventh layer with the compound (CB-3) of the present invention in an equimolar amount. (Samples 109 to 116) Samples 109 to 116 were manufactured by replacing (CB-18) of Sample 102 as shown in Table 2. (Samples 117 to 119) The amount of silver in each layer of Sample 101 was set to 15
% For sample 117 and 10% and 25% for samples 118 and 119, respectively.

[0323]

[Chemical 90]

[0324]

[Chemical Formula 91] These samples were prepared by simultaneously coating 14 layers.

Table 2 shows the silver content and the total dry film thickness of these samples. Further, when the specific photographic sensitivity defined in the present invention was determined, it was between 110 and 125 for all the samples. Further, after red imagewise exposure was applied to these samples, uniform red exposure was applied so that the cyan density of the green unexposed portion of the sample 101 was 0.6, and the following processing was performed to obtain a magenta density of 1.5. The value obtained by subtracting the syn concentration at the magenta fog portion from the cyan concentration at the point of giving is determined as the color turbidity. The sharpness is also treated in the same manner to obtain a conventional MTF (Modulation Transfer).
magenta image 20 measured by the r function method.
The MTF value in cycles / mm was determined.

Further, white light of 40 lux · sec was given to these samples, and the following development processing for obtaining a specific photographic sensitivity was carried out except that the bleaching time was changed to 30 seconds, 40 seconds and 2 minutes.
The magenta density was measured. Bleaching time 30 seconds and 40
The value obtained by subtracting the density of 2 minutes from the magenta density of second is shown in Table 2 as the desilvering defective density.

The development processing was carried out by the following method using an automatic processor (the cumulative replenishment amount of the solution was 3 times the capacity of the mother liquor tank).
Processed).

Treatment Method Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 2 minutes 45 seconds 40 ° C 45ml 10 liters Bleach 1 minute 00 seconds 38 ° C 20ml 4 liters Bleach fixing 3 minutes 15 seconds 38 ° C 30ml 8 liters Water Washing (1) 40 seconds 35 ℃ 4 liters from (2) to (1) Countercurrent piping method Water washing (2) 1 minute 00 seconds 35 ℃ 30 ml 4 liters Stability 40 seconds 38 ℃ 20 ml 4 liters Drying 1 minute 15 seconds 55 ° C Replenishment amount per 35 mm width 1 m length Next, the composition of the treatment liquid is described. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.10 (bleaching solution) mother liquor, replenisher common (Unit: g) 1,3-Diaminopropane ferric acetate 40.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator [(CH ₃ ) ₂ NCH ₂ CH ₂ -S] ₂ -2HCl Addition of 0.001 mol water 1.0 liter pH 5.5 (bleach-fixing solution) Common for mother liquor and replenisher (unit: g) Disodium salt 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia water (27%) 6.0 ml Water is added to 1.0 liter pH 7.2 (Washing solution) Mother liquor and replenisher Common tap water Water was passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400) to obtain calcium and The magnesium ion concentration was adjusted to 3 mg / liter or less, and subsequently, 20 mg / liter of sodium isocyanurate dichloride and 0.15 g / liter of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5. (Stabilizer) Mother liquor, replenisher common (unit: g) Formalin (37%) 1.0 ml Pyrazole 4.0 Polyoxyethylene-p-monononyl phenyl ether (Average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0 Liter pH 0.5-8.0

[0329]

[Table 2] From Table 2, it is clear that the samples of the present invention are excellent in sharpness represented by MTF value, color reproducibility represented by color turbidity, and good desilvering property. Further, it can be seen that the effect of the present invention is greater when the silver content is low. Example 2 Gamma and color turbidity were determined in Normal Treatment I shown in Table 3 below and Short-Time Treatment II shown in Table 4 below. The color turbidity was determined by the same method as in Example 1. Gamma was obtained as the slope of a straight line connecting the points of cyan density (fog + 0.2) and the point of (fog + 1.2). Further, Table 5 shows the difference in magenta density between the treatment II in which a white light of 40 lux · sec was applied and the treatment II in which the silver was sufficiently desilvered, as the desilvering defective concentration.

[0330]

[Table 3] (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 6.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.0 0.2 Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 4.2 4- [N-ethyl- N-β-hydroxyethylamino] 4.7 7.5-2-methylaniline sulfate (0.015 mol) (0.024 mol) Water was added to 1.0 liter 1.0 liter pH 10.00 10.20 (bleaching solution) Mother liquor (g) Replenisher (g) 1 , 3-Diaminopropane tetraacetic acid ferric salt 140 140 Ethylenediaminetetraacetic acid 4.0 5.0 Ammonium bromide 160.0 220.0 Ammonium nitrate 30.0 50.0 Ammonia water (27%) 20.0 ml 23.0 ml Acetic acid (90%) 35.0 50.0 Hydroxyacetic acid (70%) 98.0 140.0 Add water 1.0 liter 1.0 liter pH 3.9 2.5 (Fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid Sodium salt 0.5 0.7 Sodium sulfite 15.0 25.0 Sodium bisulfite 5.0 10.0 Ammonium thiosulfate aqueous solution (700 g / liter) 270.0 ml 320.0 ml Water is added 1.0 liter 1.0 liter pH 6.7 6.6 (Stabilizing liquid) Mother liquor, replenishing liquid Common (unit: g) Water Water 1.0 liter Formalin (37%) 1.2 ml 5-chloro-2-methyl-4-isothiazolin-3-one 6.0 ml 2-Methyl-4-isothiazolin-3-one 3.0 ml Surfactant [C ₁₀ H ₂₁ -O _{- (CH 2 CH 2 O)} 10 -H] 0.4 ethylene glycol 1.0 pH 7.0

[0331]

[Table 4] (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 2.0 4.0 Potassium carbonate 35.0 42.0 Potassium bromide 1.4 0.0 Potassium iodide 1.2 mg Hydroxylamine sulfate 2.0 3.8 4- [N-ethyl- N-β-hydroxyethylamino] 6.0 8.8-2-methylaniline sulfate (0.019 mol) (0.028 mol) 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.05 0.08 1-phenyl- 4-Methyl-4-hydroxymethyl-3-pyrazolidone 0.005 0.01 Water was added to 1.0 liter 1.0 liter pH 10.55 10.80 (bleaching solution, fixing solution, stabilizing solution) Same as Treatment I. Treatment III Same as Treatment II except that the bleaching time and the fixing time of Treatment II were 3 minutes and 3 minutes, respectively.

From Table 5, it is clear that the samples of the present invention have little processing dependence of gamma and color turbidity, have good short-time processability, and are excellent in color reproducibility and desilvering property. ..

[0333]

[Table 5] Example 3 The emulsion of each emulsion layer of Sample 101 was changed to Sample 3 as follows.
01 was produced.

Numbers represent silver coating amounts, which are the same as those of Sample 101 in each layer. Third layer (low sensitivity red sensitive emulsion layer) Emulsion B 0.20 Emulsion C 0.25 Fourth layer (medium sensitive red sensitive emulsion layer) Emulsion D 0.30 Emulsion I 0.25 Fifth layer (high sensitive red sensitive emulsion Emulsion layer) Emulsion A 0.30 Emulsion F 0.25 7th layer (low sensitivity green sensitive emulsion layer) Emulsion I 0.15 Emulsion K 0.15 8th layer (medium sensitivity green sensitive emulsion layer) Emulsion G 0.30 Emulsion B 0.20 9th layer (high sensitivity green sensitive emulsion layer) Emulsion F 0.35 Emulsion H 0.10 11th layer (low sensitivity blue sensitive emulsion layer) Emulsion J 0.30 Emulsion K 0.10 12th layer (High-sensitivity blue-sensitive emulsion layer) Emulsion H 0.35 Emulsion A 0.10 Thirteenth layer (first protective layer) Emulsion E 0.15 Emulsions A to K are summarized in Table 6 below.

Samples 302 to 318 were prepared by the same procedure as that for preparing samples 102 to 118 from sample 101.
The specific photographic speed of these samples was between 400 and 440.

These samples 301 to 318 were used in Examples 1 and 2.
When the same evaluation as above was performed, the effect of the present invention was confirmed.

[0337]

[Table 6]

[0338]

The silver halide color photographic light-sensitive material of the present invention has (a) excellent sharpness and color reproducibility, (b) excellent processing dependence and desilvering property, and (c) low cost and high image quality. It has a remarkable effect of being excellent.

Claims (5)

[Claims] 1. A halogenated product having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer on a support, and having a dry film thickness of 22 μm or less. A silver color photographic light-sensitive material comprising a coupler represented by the general formula (I) shown in the following chemical formula 1 and / or the general formula (II) shown in the following chemical formula 2. .. [Chemical 1] (Wherein A represents a coupler residue or a redox group, L
₁ and L ₃ represent a divalent timing group, L ₂ is 3
It represents a timing group having a valent or higher valent bond, and PUG represents a photographically useful group. j and n each independently represent 0, 1 or 2, m represents 1 or 2, s is a valence of L ₂ minus 1, and is an integer of 2 or more. When a plurality of L ₁ , L ₂ or L ₃ are present in the molecule, they may all be the same or different. Further, the plurality of PUGs may be the same or different. ) [Chemical 2] (In the formula, A and PUG have the same meanings as in the general formula (I). L ₄
Is an —OCO— group, an —OSO group, an —OSO ₂ — group —, —
OCS-group, SCO-group, -SCS-group or -WCR
₁₁ represents a R ₁₂ -group. Where W is an oxygen atom, a sulfur atom or a tertiary amino group (-NR ₁₃ -) represents, R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a substituent,
R ₁₃ represents a substituent. In addition, each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and includes a case where they are linked to each other to form a cyclic structure. L ₅ represents a group that releases PUG by electron transfer along a conjugated system or a group defined by L ₄ . ) 2. The formula weight of the residue excluding the groups represented by A and PUG in the general formula (I) and the general formula (II) is 64 or more and 240 or less. Silver halide color photographic light-sensitive material. 3. The silver halide according to claim 1 or 2, wherein the total silver content of the photographic light-sensitive material is 1.0 g / m ² or more and 4.9 g / m ² or less. Color photographic light-sensitive material. 4. The silver halide color photographic light-sensitive material according to claim 1 or 3, wherein the specific photographic sensitivity of the photographic light-sensitive material is 80 or more and less than 800. 5. The silver halide color photographic light-sensitive material according to claim 1 is subjected to color development processing containing an aromatic primary amine developing agent, desilvering processing, and then washing with water. And / or a color processing step of performing stabilizing processing, wherein the processing time of the color developing step is 150 seconds or less.