JP3150817B2 - Silver halide color photographic materials - Google Patents

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, and more particularly, to a silver halide color photographic material having high sensitivity, excellent graininess and high color reproduction. It relates to a photosensitive material.

[0002]

2. Description of the Related Art The technical progress of silver halide color light-sensitive materials for photography (including color negative and color reversal light-sensitive materials; hereinafter simply referred to as color negatives) has been continuing without any delay. The so-called photosensitive material having an ISO sensitivity of 400 class is used as a regular film for general users, and is also being used for a film with a lens (so-called image). ISO
The main reason why a photosensitive material having a sensitivity of 400 class is used for a film with a lens is that color reproduction with high chroma has become possible as well as improvement in graininess.

Hitherto, it has been known to utilize an interlayer suppression effect as a means for increasing the color saturation of a color photographic light-sensitive material. In the case of a color negative photosensitive material, by giving a development suppression effect (hereinafter referred to as an interlayer suppression effect) from the green-sensitive layer to the red-sensitive layer, the color development of the red-sensitive layer in white exposure is more than that in red exposure. Can also be suppressed.
In the color negative paper system, the gradation is balanced so that when exposed with white light, the gray level is reproduced on a color print, so the above-described interlayer suppression effect is higher than in the case of gray exposure when exposed to red. As a result of providing the cyan color of the density, it is possible to provide a more saturated red reproduction with suppressed cyan color on a print. Similarly, the effect of suppressing the interlayer from the red-sensitive layer to the green-sensitive layer gives a green reproduction with a high degree of saturation.

Utilizing this effect, Japanese Patent Application Laid-Open No. 1-182847 discloses a color photographic light-sensitive material having high chroma, excellent color reproducibility and tone reproducibility. This patent describes in detail a method of imparting an interlayer suppressing effect, but does not describe anything about the sensitivity of the photosensitive material. ISO sensitivity 1 slightly estimated from the example
It is estimated to be around 00.

[0005]

SUMMARY OF THE INVENTION The present inventors considered the further development of a film system with a lens and conducted a survey on the actual condition of a film with a lens photographed in the market.
Underexposure, so-called under-negatives, was scattered. The present inventors have investigated the exposure level of the subject of the film with the lens in more detail, and found that not only negative photography such as in cloudy weather, morning and evening, which tends to be insufficient in light quantity, but also negative exposure in photography using a strobe. I found that there are many. The cause of underexposure in flash photography is clearly indicated on the product in the range that can be photographed.However, in the event of actual photography, the image may be photographed at a distance exceeding that distance. It indicates what is required.

As described above, the problems with the current film system with a lens are that the sensitivity of the photosensitive material is still insufficient, and that the sensitivity tends to be under-negative, and the under-negative has low color saturation. It has been found that a print that satisfies the user cannot be obtained, and that it is extremely important to improve sensitivity and color saturation.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have developed a color photographic light-sensitive material having at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer on a support, The magnitude IE (X / Y) of the interlayer suppression effect is 0.15 <IE (R / G), −0.05 <IE (R /
B) 0.10 <IE (G / R), 0.15 <IE (G / R)
B) 0.03 <IE (B / G), 0.03 <IE (B / G)
R) and a characteristic photographic sensitivity of 640 to 2,000. The silver halide color photographic light-sensitive material as described in (1), comprising a compound represented by the following general formula (1) and / or general formula (2). Formula _{(1) A- (L 1)} j - (L 2) m - in _{[(L 3) n -PUG]} s formula, A represents a coupler residue or a redox group, L ₁
And L ₃ represents a divalent timing group; L ₂ represents a timing group having a trivalent or higher bond;
UG represents a photographically useful group. j and n each independently represent 0, 1 or 2; m represents 1 or 2;
It is a number obtained by subtracting 1 from the valence of ₂ , and represents an integer of 2 or more.
When a plurality of L ₁ , L ₂ or L ₃ are present in a molecule, they may be all the same or different. The plurality of PUGs may all be the same or different. In the general formula _{(2) A-L 4 -L} 5 -PUG formula, A and PUG are as in formula (1) synonymous. L ₄ represents a —OCO— group, a —OSO— group, a —OSO ₂ — group, a —OC
S-group, -SCO- group, -SCS- group or -WCR ₁₁
R ₁₂ represents a group. Here, W represents an oxygen atom, a sulfur atom or a tertiary amino group (—NR ₁₃ —), and R ₁₁ and R ₁₂
Each independently represents a hydrogen atom or a substituent, and R ₁₃ represents a substituent. And any two of R ₁₁ , R ₁₂ and R ₁₃
One represents a divalent group, and includes the case where they are linked to form a cyclic structure. And L ₅ represents a group defined by a group or L ₄ releases PUG by electron transfer along a conjugated system. Or the silver halide color photographic light-sensitive material described in or above, comprising a yellow colored cyan coupler. The silver halide grains of the all red-sensitive layer and / or the all-green sensitive layer contain silver halide grains having an average iodine content of 2 to 5 mol%. Silver halide color photographic light-sensitive material. The highest-sensitivity layer of the red-sensitive layer and the green-sensitive layer contains a selenium-sensitized tabular silver halide emulsion in which 50% or more of the total projected area has dislocation lines having an aspect ratio of 3 or more and is selenium-sensitized. Or the silver halide color photographic light-sensitive material according to any one of the above. Has confirmed that the object of the present invention is achieved.

The present invention is a further development of the technique for imparting an interlayer suppressing effect described in JP-A-1-182847, but is technically different in the following points. First, the iodine content of the silver halide emulsion was thoroughly reviewed. If the iodine content of the emulsion is increased, an interlayer suppression effect by suppressing iodine ions can be provided.On the contrary, it is found that the interlayer suppression effect is hardly received, and the setting of the present invention, that is, the all red-sensitive layer and The average iodine content of the silver halide grains in the all-green sensitive layer is from 2 to 5
Mole% is reasonable. Secondly, a DIR compound represented by the general formula (1) and / or the general formula (2) is newly introduced. This makes it possible to increase the effect of suppressing the interlayer from the red-sensitive layer to another layer.
Further, by appropriately setting the iodine content of silver halide in the green-sensitive layer emulsion, it is possible to dramatically improve the interlayer suppression effect from the red-sensitive layer to the green-sensitive layer. Thirdly, the interlayer suppression effect is increased by enhancing the masking from the red-sensitive layer to the blue-sensitive layer by the yellow colored cyan coupler. Between the red sensitive layer and the blue sensitive layer,
Usually, a green-sensitive layer is present, and it is extremely difficult to increase the interlayer suppression effect from the red-sensitive layer to the blue-sensitive layer using only the DIR compound.

In general, when the saturation is increased by utilizing the interlayer suppression effect, there is a trade-off between the sensitivity and the color saturation, and the effect of the present invention can be obtained by simply increasing the interlayer suppression effect. It is difficult to get. The present invention provides, in addition to the above-described technology for imparting an interlayer suppression effect, the sensitivity and sensitivity of silver halide emulsions.
This was made possible only by combining the granularity improvement technology. The development temperature of a color negative is usually as high as 38 ° C., and the development of the upper blue-sensitive layer tends to proceed, while the development of the lower layer, particularly the red-sensitive layer, is delayed. Therefore, it was difficult to impart and control the interlayer suppressing effect from the lower red-sensitive layer to the upper layer.
It was possible to make it possible even with an ultra-high sensitivity photosensitive material of 0 or more.

Hereinafter, the present invention will be described in detail. The silver halide color photographic light-sensitive material of the present invention must have a specific photographic sensitivity of 640 or more. More preferably, it is 640 or more and 2000 or less. The specific photographic sensitivity mentioned here is a sensitivity determined according to the definition described in JP-A-63-226650, and is a sensitivity similar to the ISO standard which is an international standard, but with less uncertainty. Therefore, the time from the exposure to the development processing is shortened, and the development processing conditions are kept constant.

Next, IE indicating the magnitude of the interlayer suppression effect is shown.
(X / Y) will be described. IE (X / Y) represents the magnitude of the interlayer suppression effect from X to Y, and is obtained by the method shown in FIG. In the figure, Y _DMIN represents the minimum density of the color-sensitive layer Y when the color-sensitive layer X is stepwise exposed.

For example, the magnitude IE (G / R) of the interlayer suppression effect from the green-sensitive layer to the red-sensitive layer is determined as follows. First, the sample was exposed stepwise with green light (Fuji Photo Film filter: BPN-55), and then red light (Fuji Photo Film filter: BPN-55).
In SC-60), a characteristic curve shown in FIG. 1 obtained by uniformly exposing to a density of R _DMIN +1.0 is obtained. In this characteristic curve, the fog density of the green-sensitive layer and the decrease in the density of the red-sensitive layer which decreases during the movement to the high-exposure side by 1.51 ogE from the exposure amount P that gives the green-sensitive layer IE (G / G /
R). The effect of suppressing the interlayer from the blue-sensitive layer to the red-sensitive layer is due to blue light (Fuji Photo Film: BPN-
45) can be similarly obtained.

IE (X / Y) can take both positive and negative values. This is due to color turbidity due to the side absorption of the color coupler, and since IE (X / Y) is a negative value, it does not mean that the interlayer suppression effect is not effective.

Next, the compounds represented by formulas (1) and (2) will be described in detail.

In the general formula (1), A represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (for example, open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide) and magenta coupler residues (for example, 5-pyrazolone type and pyrazolotriazole). Type or imidazopyrazole type coupler residue), cyan coupler residue (for example, phenol type, naphthol type, imidazole type or 30 type described in EP-A-249,453).
Coupler residues such as pyrazolopyrimidine type described in U.S. Pat. No. 4,001) and colorless coupler residues (e.g., coupler residues such as indanone type or acetophenone type). Also, U.S. Pat. Nos. 4,315,070, 4,183,752, 4,174,969, 3,961,959, 5,171,223 and JP-A-52-82423. Or a heterocyclic coupler residue described in (1).

When A represents a redox group, the redox group is a group which can be cross-oxidized by an oxidized form of a developing agent, and examples thereof include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, , 2-naphthohydroquinones, sulfonamidophenols,
Hydrazides or sulfonamido naphthols are exemplified. These groups are specifically described in, for example, JP-A-61-2.
No. 30135, No. 62-251746, No. 61-27
No. 8852, U.S. Pat. Nos. 3,364,022, 3,
379,529, 3,639,417, 4,6
No. 84,604 or J. Org. Chem., 29, 588 (1964)
It is described in.

In the general formula (1), L ₁ is preferably the following. (1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396;
249148 and 60-249149, and are groups represented by the following general formula (T-1). Here symbol * represents the position at which the group bonds to A or L ₁ in the general formula (I) compounds represented by the mark ** represents a position bonded with L ₁ or L _2. 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 are a hydrogen atom Or represents 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, and typical examples of R ₁₃ are an R ₁₅ group, R ₁₅ CO—
R ₁₅ SO ₂ —, R ₁₅ (R ₁₆ ) NCO— or R
₁₅ (R ₁₆ ) NSO ₂ — groups. 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. R ₁₁ ,
The case where any two of R ₁₂ and R ₁₃ represent a divalent group and form a cyclic structure by linkage is also included. General formula (T-1)
Specific examples of the group represented by include the groups shown below.

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

(2) A group capable of causing a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction. For example, a timing group described in US Pat. No. 4,248,292 may be mentioned. Can be represented by Formula (T-2) * -Nu-Link-E-** In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, and Nu represents A group that can undergo a more nucleophilic attack to cleave the bond with the ** mark,
Link represents a linking group that sterically links Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by the general formula (T-2) include, for example, groups shown below.

[0023]

Embedded image

[0024]

Embedded image

(3) A group which 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.
1,845, JP-A-57-188035, and 58-
No. 98728, No. 58-209736, No. 58-20
9737, 58-209736 and the like,
It is a group represented by the following general formula (T-3).

[0026]

Embedded image

In the formula, *, **, W, R ₁₁ , R ₁₂ and t have the same meanings as described for formula (T-1). However, R ₁₁ and R ₁₂ may combine to form a benzene ring or a heterocyclic ring. R ₁₁ or R ₁₂ and W may combine to form a benzene ring or a heterocyclic ring. 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
X is 1 when is a carbon atom, and x is 0 when Z ₁ is a nitrogen atom. Relationship between Z ₂ and y is the same as the relationship between Z ₁ and x. Further, t represents 1 or 2, and when t is 2, two-[Z ₁ (R ₁₁ ) _x = Z ₂ (R ₁₂ ) _y ]-may be the same or different. The -CH ₂ adjacent to the mark ** - group may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms.

Specific examples of the formula (T-3) are shown below.

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

(4) Group utilizing cleavage reaction by hydrolysis of ester For example, a linking group described in West German Patent Publication No. 2,626,315, which has the following general formulas (T-3) and (T-
And groups represented by 4). General formula (T-4) * -OCO-** General formula (T-5) * -SCS-** In the formulas, * and ** have the same meanings as described for General formula (T-1). It is. (5) Group utilizing cleavage reaction of imino ketal A linking group described in US Pat. No. 4,546,073, for example, a group represented by the following general formula (T-6).

[0034]

Embedded image

In the formula, *, ** and W represent the general formula (T
-1) have the same meaning as described in, R ₁₄ is R
Represents the same meaning as ₁₃ . Specific examples of the group represented by the general formula (T-6) include the following groups.

[0036]

Embedded image

In the general formula (1), L ₁ is preferably represented by any _one of the general formulas (T-1) to (T-5), and particularly preferably the general formulas (T-1) and (T-3). ) And (T-4).

In the general formula (1), j is preferably 0 or 1.

In the general formula (1), the group represented by L ₂ represents a trivalent or higher valent timing group, and preferably a group represented by the following general formula (TL ₁ ) or (TL ₂ ) It is. Formula _{(T-L 1) * -W-} [Z 1 (R 11) x = Z 2 (R 12) y] t -CH 2 - *
* In the formula, W, Z ₁ , Z ₂ , R ₁₁ , R ₁₂ , x, y and t represent the same meaning as described for the general formula (T-3).
The symbol * represents a position bonding to A- (L ₁ ) _j- in the general formula (1), and the symbol ** represents a position bonding to-(L ₃ ) _n -PUG. However, at least one of a plurality of R ₁₁ or R ₁₂ is a substituted or unsubstituted methylene group and-(L
₃ ) represents a group bonded to _n- PUG.

The formula (T-L ₁ ) is preferably W
Represents a nitrogen atom, and more preferably W and Z
_Two are bonded to form a 5-membered ring, particularly preferably an imidazole or pyrazole ring. In the general formula (T-L ₂ ) *-N- (Z ₃ -**) ₂ , the symbols * and ** have the same meanings as those in the general formula (TL ₁ ). The Z ₃ group represents a substituent or an 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.

The general formulas (T-L ₁ ) and (T-L ₁ )
Specific examples of L ₂ ) will be given below, but the present invention is not limited thereto.

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

However, the groups mentioned in the specific examples may further have a substituent, such as an alkyl group (eg, methyl, ethyl, isopropyl, t-butyl, hexyl, methoxy) Methyl, methoxyethyl, chloroethyl, cyanoethyl, nitroethyl,
Hydroxypropyl, carboxyethyl, dimethylaminoethyl, benzyl, phenethyl), aryl groups (e.g., phenyl, naphthyl, 4-hydroxyphenyl, 4-
Cyanophenyl, 4-nitrophenyl, 2-methoxyphenyl, 2,6-dimethylphenyl, 4-carboxyphenyl, 4-sulfophenyl), a heterocyclic group (for example, 2
-Pyridyl, 4-pyridyl, 2-furyl, 2-thienyl, 2-pyrrolyl), a halogen atom (eg, chloro, bromo), a nitro group, an alkoxy group (eg, methoxy, ethoxy, isopropoxy), an aryloxy group (phenoxy) An alkylthio group (eg, methylthio, isopropylthio, t-butylthio), an arylthio group (eg, phenylthio), an amino group (eg, amino, dimethylamino, diisopropylamino), an acylamino group (eg, acetylamino, benzoylamino), a sulfonamide group ( For example, methanesulfonamide, benzenesulfonamide), cyano group, carboxyl group, alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (for example, phenoxycarbonyl). Carbamoyl group (e.g. N- ethylcarbamoyl, N- phenylcarbamoyl) can be mentioned.

Among them, 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.

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 (1), m is preferably 1.

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

In the general formula (1), n is preferably 0 or 1, and particularly preferably 0.

The photographically useful group represented by PUG in the formula (1) is, for example, a development inhibitor, a dye, a fogging agent, a developing agent, a coupler, a bleaching accelerator and a fixing accelerator. Examples of preferred photographically useful groups are described in U.S. Pat. No. 4,248,96.
A photographically useful group described in No. 2 (in the patent, the general formula PU
G), a dye described in JP-A-62-49353 (a part of a leaving group released from a coupler in the specification), and a development described in U.S. Pat. No. 4,477,563. And a bleaching accelerator described in JP-A-61-201247 and JP-A-2-55 (the part of the leaving group released from the coupler in the specification). In the present invention, particularly preferred as a photographically useful group is a development inhibitor.

As the development inhibitor, groups represented by the following formulas (INH-1) to (INH-13) are preferred.

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

In the general formula (INH-6), R ₂₁ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group (eg, methyl, ethyl, propyl, phenyl).

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

In the formula, * represents the L of the compound represented by the general formula (1).
Represents a position bonded with the group represented by ₂ or L _3.

** represents a position to be bonded to a substituent, and the substituent is a substituted or unsubstituted alkyl group;
Examples include an aryl group, a heterocyclic group, an alkylthio group, an alkyl or an aryloxycarbonyl group, and it is preferable that a group that decomposes in a processing solution during photographic processing is included in these substituents.

Specific examples of the substituted or unsubstituted alkyl group include methyl, ethyl, propyl, butyl, hexyl, decyl, isobutyl, t-butyl, 2-ethylhexyl, 2-methylthioethyl, benzyl, 4-methoxybenzyl, Phenethyl, 1-methoxycarbonylethyl, propyloxycarbonylmethyl, 2- (propyloxycarbonyl) ethyl, butyloxycarbonylmethyl, pentyloxycarbonylmethyl, 2-cyanoethyloxycarbonylmethyl, 2,2-dichloroethyloxycarbonylmethyl, -Nitropropyloxycarbonylmethyl, 4-nitrobenzyloxycarbonylmethyl, 2,5-dioxo-3,6-dioxadecyl and the like.

Examples of the substituted or unsubstituted aryl group include phenyl, naphthyl, 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 2-methylthiophenyl, 3-methoxycarbonylphenyl,
(2-cyanoethyloxycarbonyl) -phenyl and the like.

Examples of the substituted or unsubstituted heterocyclic group include 4-pyridyl, 3-pyridyl, 2-pyridyl, 2-furyl, 2-tetrahydropyranyl and the like. Examples of the substituted or unsubstituted alkylthio group include methylthio, t
-Butylthio, 1-methoxycarbonylethylthio and the like. Examples of the substituted or unsubstituted alkyl or aryloxycarbonyl group include methoxycarbonyl, butoxycarbonylmethoxycarbonyl, isopentyloxycarbonylmethoxycarbonyl, N-hexylcarbamoylmethoxycarbonyl, phenoxycarbonyl and the like.

Of these, preferred as INH (development inhibitor) are those represented by formulas (INH-1), (INH-2) and
(INH-3), (INH-4), (INH-9) and (INH-12), and particularly preferably the general formula (I)
NH-1), (INH-2) and (INH-3).

The substituent bonded to INH is preferably an alkyl group, a substituted or unsubstituted phenyl group or an alkyl or aryloxycarbonyl group.

The compound represented by the general formula (1) is particularly preferably a compound represented by the following general formula (1a) or (1b).

General formula (1a) A- (L ₁ ) _j -W- [Z ₁ (R ₁₁ ) _x = Z ₂ (R ₁₂ ) _y ] _t -CH ₂ -PUG General formula (1b) A-L ₁ -N- (Z ₃ -PUG) ₂ The symbols in the formulas represent the general formulas (1), (T-L ₁ ) and (T-
This is synonymous with L ₂ ). In the general formula (1a), j is preferably 0 or 1. In the general formulas (1a) and (1b), L ₁ is preferably a —OC (＝ O) — group, and PUG is preferably a development inhibitor.

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 a function of a development inhibitor, a dye, a fogging agent, a developing agent, a coupler, a bleaching accelerator, a fixing agent, or the like.

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

Next, the compound represented by formula (2) will be described. In the general formula (2), A and PUG are the general formulas
Synonymous with (1). L ₄ represents a —OCO— group, —OSO—
Group, -OSO ₂ - group, -OCS- group, -SCO- group, -
Represents an SCS— group or a —WCR ₁₁ R ₁₂ — group. Here, W, R ₁₁ and R ₁₂ are L of the compound represented by the general formula (1).
It is synonymous with Formula (T-1) in the definition in _one explanation.

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 an —OCH ₂ — group or W. And R ₁₁ or R ₁₂ represent a group forming a ring.

[0078] The L ₄ is -WCR ₁₁ R ₁₂ - may represent other groups, preferably -OCO- group, -OSO- group, -O
An SO ₂ — group, particularly preferably an —OCO— group.

The group represented by L ₅ represents a group which releases PUG by electron transfer along a conjugated system or a group defined by L ₄ . Group which releases PUG by electron transfer along a conjugated system has the same meaning as the groups represented by the general formula (1) formula in the description of L ₁ of (T-3). L ₅ is preferably a group that releases PUG by electron transfer along a conjugated system,
More preferably, it is a group capable of bonding to L ₄ with a nitrogen atom.

Among the compounds represented by the general formula (2), preferred are the compounds represented by the following general formulas (3) and (4).

[0081]

Embedded image

In the general formula (3), A has the same meaning as in the general formula (1). 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 ₁₀₅ is an unsubstituted phenyl group, primary alkyl group,
A primary alkyl group substituted with a group other than an alkylthio group and an aryl group, or —CO ₂ C (R ₁₀₇ ) (R ₁₀₈ ) CO ₂ R
Represents a group represented by ₁₀₆ . Here, R ₁₀₆ represents an unsubstituted alkyl group, and R ₁₀₇ and R ₁₀₈ each independently represent a hydrogen atom or an unsubstituted alkyl group. However, at least one of R _{101 to} R ₁₀₄ is a substituent other than a hydrogen atom.

[0083]

Embedded image

In the general formula (4), A, INH and R
₁₀₅ has the same meaning as in formula (3). R ₁₁₁ , R ₁₁₂ and R
₁₁₃ represents a hydrogen atom or an organic group, and R ₁₁₁ ,
Any two of R ₁₁₂ and R ₁₁₃ may be linked to form a divalent group to form a ring.

The compound represented by formula (3) will be described in more detail.

In the general formula (3), A has the same meaning as in the general formula (1). 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) and an alkyl group (eg, methyl, ethyl, isopropyl, propyl, tert- Butyl,
tert-amyl, isobutyl, sec-butyl, octyl,
Methoxymethyl, 1-methoxyethyl, 2-chloroethyl, nitromethyl, 2-cyanoethyl, 2-carbamoylethyl, 2-dimethylcarbamoylethyl), a halogen atom (eg, fluoro, chloro, bromo, iodo),
An alkoxy group (eg, methoxy, ethoxy, isopropyloxy, propyloxy, tert-butyloxy, isobutyloxy, butyloxy, octyloxy, 2-methoxyethoxy, 2-chloroethoxy), an aryloxy group (eg, phenoxy, naphthoxy, p-methoxyphenoxy) ), Alkylthio groups (eg, methylthio, ethylthio, isopropylthio, propylthio, tert-butylthio, isobutylthio, sec-butylthio, octylthio, 2-methoxyethylthio), arylthio groups (eg, phenylthio, naphthylthio, p-methoxyphenylthio), Amino groups (eg, amino, methylamino, phenylamino, dimethylamino, diethylamino, diisopropylamino, phenylmethylamino), carbamoyl groups (eg, Yl, methylcarbamoyl, dimethylcarbamoyl, diethylcarbamoyl, diisopropylcarbamoyl, ethylcarbamoyl, isopropylcarbamoyl, tert-butylcarbamoyl, phenylcarbamoyl, phenylmethylcarbamoyl), sulfamoyl group (for example, sulfamoyl, methylsulfamoyl, ethylsulfamoyl, isopropyl) Sulfamoyl, phenylsulfamoyl, octylsulfamoyl, dimethylsulfamoyl, diethylsulfamoyl, diisopropylsulfamoyl, dihexylsulfamoyl, phenylmethylsulfamoyl), alkoxycarbonyl group (for example, methoxycarbonyl, propyl Oxycarbonyl, isopropyloxycarbonyl, te
rt-butyloxycarbonyl, tert-amyloxycarbonyl, octyloxycarbonyl), aryloxycarbonyl group (for example, phenoxycarbonyl, p-methoxyphenoxycarbonyl), acylamino group (for example, acetylamino, propanoylamino, pentanoylamino, N- Methylacetylamino, benzoylamino), sulfonamide groups (for example, methanesulfonamide, ethanesulfonamide, pentanesulfonamide,
Benzenesulfonamide, p-toluenesulfonamide), alkoxycarbonylamino group (for example, methoxycarbonylamino, isopropyloxycarbonylamino, tert-butoxycarbonylamino, hexyloxycarbonylamino), aryloxycarbonylamino group (for example, phenoxycarbonylamino), A ureido group (for example, 3-methylureido, 3-phenylureido), a cyano group, a nitro group and the like 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. Preferred substituents include an alkyl group, a halogen atom and an alkoxy group, and an alkyl group is preferred.

In the general formula (3), 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, ethyl, isopropyl, tert-butyl, isobutyl, hexyl, 2-
Methoxyethyl is mentioned. R ₁₀₃ and R ₁₀₄ are preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.

In the general formula (3), the group represented by R ₁₀₅ is a primary alkyl group substituted with a group other than an unsubstituted phenyl group, a primary alkyl group, an alkylthio group, an aryl group, or —CO ₂ C (R ₁₀₇ ) (R ₁₀₈ ) CO ₂ represents a group represented by R ₁₀₆ . Examples of the alkyl group include ethyl,
Examples include propyl, butyl, isobutyl, pentyl, isopentyl, 2-methylbutyl, hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-ethylbutyl, heptyl, and 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, an ureido group, a cyano group, and a nitro group. Specific examples of each group include those exemplified as the substituents for R ₁₀₁ and R ₁₀₂ except for 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). R ₁₀₇ , R ₁₀₈
Represents a hydrogen atom, an unsubstituted alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl);
R ₁₀₇ and R ₁₀₈ may be the same or different.

Further, R ₁₀₅ may be substituted with two or more substituents. The substituent of R ₁₀₅ is preferably fluoro, chloro, alkoxy, carbamoyl, alkoxycarbonyl, cyano or nitro.
Among these, an alkoxycarbonyl group is particularly preferred.

R ₁₀₅ is preferably a phenyl group,
Or a primary unsubstituted alkyl group having 2 to 6 carbon atoms,-
_{CO 2 C (R 107) (} R 108) CO 2 in R ₁₀₆ R ₁₀₆ is moreover R ₁₀₇ is an unsubstituted alkyl group having 6 C 3 -C,
R ₁₀₈ is a group consisting of both hydrogen atoms, or a primary alkyl group substituted by the groups mentioned above as preferred substituents of R ₁₀₅ . Particularly preferably, it has 1 to 3 carbon atoms.
It is a primary unsubstituted alkyl group or a primary alkyl group substituted with an alkoxycarbonyl group.

In the general formula (3), the group represented by INH represents a group having a development inhibitor.
General formulas (INH-1) to (P) described in (1).
(INH-13). The preferred range etc. are also represented by the general formula
Same as (1).

Next, the compound represented by formula (4) 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). Preferably, at least one of R ₁₁₂ and R ₁₁₃ is a hydrogen atom.
_This is when ₁₁₂ and R ₁₁₃ are hydrogen atoms.

R ₁₁₁ represents an organic group, and is preferably the following groups. Alkyl groups (eg, methyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, neopentyl, hexyl), aryl groups (eg, phenyl), acyl groups (eg, acetyl, benzoyl),
A sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), a carbamoyl group (eg, ethylcarbamoyl, phenylcarbamoyl), a sulfamoyl group (eg, ethylsulfamoyl, phenylsulfamoyl),
Alkoxycarbonyl group (for example, ethoxycarbonyl,
Butoxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl, 4-methylphenoxycarbonyl), an alkoxysulfonyl group (eg, butoxysulfonyl, ethoxysulfonyl), an aryloxysulfonyl group (eg, phenoxysulfonyl, 4-methoxyphenoxysulfonyl), a cyano group Nitro group, nitroso group, thioacyl group (eg, thioacetyl, thiobenzoyl), thiocarbamoyl group (eg, ethylthiocarbamoyl), imidoyl group (eg, N-ethylimidoyl), amino group (eg, amino, dimethylamino, methylamino) An acylamino group (eg, formylamino, acetylamino, N-methylacetylamino), an alkoxy group (eg, methoxy, isopropyloxy),
Or an aryloxy group (for example, phenoxy).

[0098] These groups may further have a substituent group, other halogen atom of the groups mentioned as R ₁₁₁ (e.g. fluoro, chloro, bromo), a carboxyl group, a sulfo group mentioned as a substituent Can be

It is preferred that R ₁₁₁ has 15 or less atoms other than hydrogen atoms.

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

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

The divalent groups are preferably the following groups.

[0104] -C (= O) -N (R 114) -, - SO 2 -
_{N (R 114) -, -} (CH 2) 3 -, - (CH 2) 4 -, - (C
_{H 2) 5 -, - C} (= O) - (CH 2) 2 -, - C (= O) -
_{N (R 114) -C (=} O) -, - SO 2 -N (R 114) -C
(= O)-, -C (= O) -C ( _R114 ) ( _R115 )-,-
(CH ₂ ) ₂ —O—CH ₂ —.

[0105] wherein R ₁₁₄ and R ₁₁₅ are as defined when the hydrogen atom or R ₁₁₁ represents a monovalent organic group, R ₁₁₄
And R ₁₁₅ may be the same or different.

The remaining groups which do not participate as a divalent group among R ₁₁₁ , R ₁₁₂ and R ₁₁₃ represent a hydrogen atom or a monovalent organic group, and specific examples of the organic group include the same groups as those described above when no ring is formed. ₁₁₁ , R ₁₁₂ and R ₁₁₃ are the same.

When any two of R ₁₁₁ , R ₁₁₂ and R ₁₁₃ are bonded to form a ring, preferably one of R ₁₁₂ and R ₁₁₃ is a hydrogen atom, and the remaining R ₁₁₂ to R ₁₁₃ are a case of forming the R ₁₁₁ and ring, more preferably when the divalent group of left mentioned earlier is attached to the nitrogen atom of the general formula (4), the right end is attached to a carbon atom.

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

In the general formulas (1) and (2), A and PUG
The formula weight of the residue excluding the group represented by is preferably from 64 to 240, more preferably from 70 to 200.
Or less, particularly preferably 90 or more and 180 or less.

The specific examples of the compounds represented by formulas (1) to (4) of the present invention are shown below, but the present invention is not limited by these.

In the formulas (1) and (A), A represents a coupler residue. In the formulas (2) to (4), A represents a coupler residue. Is the number prefixed with (CB),
In (1) to (4), those in which A represents a redox group are indicated by numbers with (SA) prefixed.

[0112]

Embedded image

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

[0136]

Embedded image

[0137]

Embedded image

[0138]

Embedded image

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

Embedded image

The synthesis of the compounds of the present invention is described, for example, in US Pat. Nos. 4,847,383, 4,770,990, 4,684,604, 4,886,736 and JP-A-60-736. Nos. 218645, 61-230135, Japanese Patent Application Nos. 2-37070, 2-170832, and 2-251192 or similar methods can be used.

A specific synthesis example will be described below. (Synthesis Example 1) Synthesis of Exemplified Compound (CA-1) The compound was synthesized by the following synthesis route.

[0149]

Embedded image

After reacting CA-1a (3.40 g) in thionyl chloride (30 ml) at 60 ° C. for 1 hour, excess thionyl chloride was distilled off under reduced pressure. This residue was subjected to CA-1b (7.
48 g) and diisopropylethylamine (10.5 ml)
Was added to a dimethylformamide solution (0 ° C.) and stirred for 1 hour. Thereafter, this solution was poured into water (500 ml), and the resulting 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) was reacted in 1,2-dichloroethane (30 ml) for 1 hour. There, CA-1e (3.20
g) in ethyl acetate (20 ml) was added under water cooling, followed by diisopropylethylamine (4.5 ml).
Stirred for hours. The reaction was stopped with 1 N hydrochloric acid, and chloroform (30 ml) was added to dilute the reaction solution. Thereafter, the reaction solution was washed with water three times, and the organic layer was dried over sodium sulfate.
The oil obtained by distilling off the organic solvent was subjected to silica gel column chromatography (ethyl acetate-hexane = 1: 5).
Compound CA-1 was purified by purification at 1.20.
g was obtained. The structure was confirmed by NMR. m. p. 13
3.0-134.0 ° C.

(Synthesis Example 2) Synthesis of Exemplified Compound (CA-12) The compound was synthesized by the following synthesis route.

[0153]

Embedded image

CA-12a (10.7 g) and a 37% formalin aqueous solution (30 ml) were reacted in acetic acid (100 ml) at 70 ° C. for 5 hours, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate-hexane 2: 1) to give CA-12b.
4 g (yield 53%) was obtained.

Next, CA-12b (3.2 g) and CA-1
2c (2.1 g) was suspended in chloroform (40 ml), and zinc iodide (5.7 g) was added thereto and reacted at room temperature for 2 hours. Stop the reaction with 1N hydrochloric acid and add 40 ml of chloroform.
After dilution with water, the reaction solution was washed twice with water. The organic layer was dried over sodium sulfate, and the residue obtained after concentration was subjected to silica gel column chromatography (ethyl acetate-hexane 1: 1).
Exemplified compound (CA-12) by purification in 4)
Was obtained in an amount of 4.1 g (yield 25%). The structure is NMR, mass,
Confirmed by elemental analysis.

(Synthesis Example 3) Synthesis of Exemplified Compound (CB-2) The compound was synthesized by the following synthesis route.

[0157]

Embedded image

CB-2a (10 mmol) was suspended in chloroform (30 ml), and thionyl chloride (20 mmol) was added thereto.
l) was added and reacted at 50 ° C. for 1 hour, and then the solvent was distilled off. The residue obtained here is added to a solution of CB-2b (10 mmol) and diisopropylethylamine (20 mmol) in dimethylformamide (30 ml), reacted for 1 hour, and then poured into ice water (200 ml). After adding 50 ml of chloroform and stirring, the aqueous phase was separated, the organic layer was further washed twice with water (100 ml), dried over sodium sulfate and concentrated to obtain CB-2c.

The resulting CB-2c was converted to chloroform (30
nitrophenyl chlorocarbonate (10 ml).
mmol) and allowed to react for 1 hour, and then CB-2b (10 mm
ol) in ethyl acetate (50 ml), and further add diisopropylethylamine (50 mmol) and react for 1 hour. After stopping the reaction by adding 1N hydrochloric acid (10 ml), the mixture was diluted with ethyl acetate (10 ml). The organic layer is 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 Exemplified Compound CB.
-2 is obtained (1.94 g, yield 23%). m. p. 1
01.5-102.5 ° C.

(Synthesis Example 4) Synthesis of Exemplified Compound (CB-3) The compound was synthesized by the following synthesis route.

[0161]

Embedded image

Compound (C-3a) as a starting material
It can be synthesized by the same method as in B-2. Yield 31%. m. p. 68.0-69.0 ° C.

(Synthesis Example 5) Synthesis of Exemplified Compound (CB-11) The compound was synthesized by the following synthesis route.

[0164]

Embedded image

200 g of (CB-11a) and (CB-11a)
b) 34.7 g was dissolved in ethyl acetate (500 ml), and diisopropylethylamine (142 ml) was added thereto.
Stirred for hours. The precipitated crystals were collected by filtration and washed with ethyl acetate to give 176 g (75%) of (CB-11c).
Obtained.

53.6 g of (CB-11c) and paraformaldehyde (27.9 g) were reacted under reflux in a mixture of 1,2-dichloroethane (500 ml) and acetic acid (54 ml) for 4 hours. After cooling to room temperature, the reaction solution was washed with water, dried over anhydrous sodium sulfate and concentrated. The resulting residue was purified by silica gel column chromatography using chloroform as an eluent to give (CB-11d) 23.2.
g (41.2%).

(CB-11d) 23.2 g and (CB-1d)
1e) 6.78 g of chloroform was dissolved in 250 ml of chloroform, 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, concentrated, and the obtained residue was purified by silica gel column chromatography (ethyl acetate-hexane 1: 4) to give an exemplary compound (CB-
7.0 g (23.9%) of 11) was obtained. m. p. 11
7.0-118.5 ° C.

(Synthesis Example 6) Synthesis of Exemplified Compound (CB-13) A compound was synthesized in the same manner as in Synthesis Example 5. m. p. 61.
5 to 63.0 ° C. (Synthesis Example 7) Synthesis of Exemplified Compound (CB-19) The compound can be synthesized by the same method as in Synthesis Example 2 of JP-A-60-218645. Yield 7%. m. p. 115
° C. (Synthesis Example 8) Synthesis of Exemplified Compound (SA-5) The compound was synthesized by the following synthesis route.

[0169]

Embedded image

11.6 g of SA-5a (synthesized in the same manner as described in JP-A-61-230135)
Was added to 30 ml of thionyl chloride 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 obtain (SA-5b) as crude crystals. Then (SA
-5b) 13.1 g was added to a solution of 7.2 g of (SA-5c) and 12.1 g of triethylamine in N, N, -dimethylformamide (100 ml) at 0 ° C, and further reacted at room temperature for 1 hour.

The reaction mixture was poured into an aqueous solution of 2N hydrochloric acid (60 ml) and ice water (300 ml), and ethyl acetate (300 ml) was added and the mixture was stirred. The liquid was transferred to a separating funnel, the oil layer was removed, and washed with water several times. The organic layer was dried over anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography (ethyl acetate-hexane = 1/4 to 1/1 (v / v) as an eluent) to give an exemplary compound. 3.7 g of SA-5 was obtained as amorphous.

The compound represented by formula (1) or (2) of the present invention may be added to any layer in the light-sensitive material, but is preferably added to the light-sensitive emulsion layer and / or a layer adjacent thereto. It is particularly preferable to add them to the red-sensitive emulsion layer and / or the green-sensitive emulsion layer. When the same color-sensitive layer is divided into two or more layers having different sensitivities, it may be added to any of the highest sensitivity layer, the lowest sensitivity layer and the intermediate sensitivity layer.

The total amount added to the light-sensitive material is 0.0
0.01 to 1.0 g / m ² , preferably 0.010 to 1.0 g / m ²
0.5 g / m ² , more preferably 0.020 to 0.40 g
/ M ² , more preferably 0.030 to 0.30 g / m ² .

When the compounds of the general formulas (1) and (2) are used in combination, the mixing ratio can be arbitrarily selected and there is no particular limitation. Further, the compound of the general formula (1) or the general formula (2) can be used in combination with a development inhibitor releasing compound other than the present invention according to the purpose.

Next, the yellow colored cyan coupler of the present invention will be described.

In the present invention, a yellow colored cyan coupler refers to a coupler having an absorption maximum in the visible absorption region of the coupler between 400 nm and 500 nm, and coupling with an oxidized aromatic primary amine developing agent to absorb visible light. A cyan coupler that forms a cyan dye having an absorption maximum in the region between 630 nm and 750 nm.

Among the yellow colored cyan couplers of the present invention, a water-soluble 6-hydroxy-2-pyridone-5-ylazo group and a water-soluble pyrazolone are obtained by a coupling reaction with an oxidized aromatic primary amine developing agent. A cyan coupler capable of releasing a compound residue containing a -4-ylazo group, a water-soluble 2-acylaminophenylazo group or a water-soluble 2-sulfonamidophenylazo group is preferably used.

The colored cyan coupler of the present invention is preferably represented by the following formulas (CI) to (CIV).

[0179]

Embedded image

In the general formulas (CI) to (CIV), Cp
Is a cyan coupler residue (T is attached to its coupling position), T is a timing group, k is an integer of 0 or 1, X is N, O, or S, and (T) represents a divalent linking group which binds to _k or Cp and links Q, and Q represents an arylene group or a divalent heterocyclic group.

In the general formula (CI), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group. , A carbonamido group, a sulfonamido group or a sulfonyl group is represented by R
₁₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, respectively. Where T, X,
At least one of Q, R ₁₁ , R ₁₂ or R ₁₃ shall contain a water-soluble group (for example, hydroxyl, carboxyl, sulfo, amino, ammonium, phosphono, phosphino, hydroxysulfonyloxy).

The following groups in the general formula (CI)

[0183]

Embedded image

It is common knowledge that the following tautomeric structures can be taken, and these tautomeric structures are also included in the structure defined by the general formula (CI) of the present invention.

[0185]

Embedded image

In the general formula (CII), R ₁₄ is an acyl group or a sulfonyl group, R ₁₅ is a substitutable group, and j is 0
Represents an integer of 1 to 3. When j is an integer of 2 or more, R ₁₅ may be the same or different. Where T, X,
At least one of Q, R ₁₄ or R ₁₅ contains a water-soluble group (eg, hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammonium).

In the general formulas (CIII) and (CIV), R
₁₆ is a hydrogen atom, a carboxyl group, a sulfo group, a cyano group,
Alkyl group, cycloalkyl group, aryl group, alkoxy group, cycloalkyloxy group, aryloxy group, heterocyclic group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, carbonamide group, sulfonamide group, or A sulfonyl group, R ₁₇ is a hydrogen atom, an alkyl group, a cycloalkyl group,
Represents an aryl group or a heterocyclic group, respectively. Where T,
At least one of X, Q, R ₁₆ or R ₁₇ shall contain a water-soluble group (eg, hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammonium).

Also, the following groups

[0189]

Embedded image

Are the same compounds in a tautomeric relationship.

The compounds represented by formulas (CI) to (CIV) will be described below in more detail.

Examples of the coupler residue represented by Cp include known cyan coupler residues (for example, phenol type and naphthol type).

The timing group represented by T has the general formula (C
A group in which the bond with Cp is cleaved by a coupling reaction between the couplers represented by I) to (CIV) and an oxidized form of an aromatic primary amine developing agent, and then the bond with X is cleaved; It is used for various purposes such as control of reactivity, stabilization of coupler, control of release timing of X or less. Examples of the timing group include the following formulas (T-1) to (T-7)
And a known linking group represented by The following formula (T-
In each group represented by 1) to (T-7), * mark represents C
The p and ** marks respectively bind to X.

[0194]

Embedded image

In the formula, R ₂₀ represents a group capable of being substituted on a benzene ring, R ₂₁ represents R ₄₁ described below, and R ₂₂ represents a hydrogen atom or a substituent. t represents an integer of 0 to 4.
As the substituent for R ₂₀ and R ₂₂ , R ₄₁ , a halogen atom,
_{R 43 O-, R 43 S-,} R 43 (R 44) NCO-, R 43 OO
_{C-, R 43 SO 2 -,} R 43 (R 44) NSO 2 -, R 43 CO
_{N (R 43) -, R} 41 SO 2 N (R 43) -, R 43 CO-,
R ₄₁ COO-, R ₄₁ SO-, nitro, R ₄₃ (R ₄₄₎ NC
ON (R ₄₅ )-, cyano, R ₄₁ OCON (R ₄₃ )-, R
_{43 OSO 2 -, R 43 (} R 44) N-, R 43 (R 44) NSO 2
N (R ₄₅ )-or a group shown below

[0196]

Embedded image

The following can be mentioned.

In the above formula, R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

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

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

The heterocyclic group is a substituted or unsubstituted 3- to 8-membered ring having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, wherein the hetero atom is selected from a nitrogen atom, an oxygen atom or a sulfur atom. It is a heterocyclic group. Representative examples of the heterocyclic group include 2-pyridine, 2-thienyl, 2-furyl, 1,3,4-thiadiazol-2-yl, 2,4
-Dioxo-1,3-imidazolidin-5-yl, 1,
Examples include 2,4-triazol-2-yl or 1-pyrazolyl.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include
Halogen atom, R ₄₇ O-, R ₄₆ S-, R ₄₇ CON
_{(R 48) -, (R} 47) (R 48) NCO-, R 46 OCON
_{(R 47) -, R 46} SO 2 N (R 47) -, (R 47)
_{(R 48) NSO 2 -,} R 46 SO 2 -, R 47 OCO -, (R
_{47) (R 48) NCON (} R 49) -, a group having the same meaning as R _46, groups shown below,

[0203]

Embedded image

Examples thereof include R ₄₆ COO—, R ₄₇ OSO ₂ —, a cyano group and a nitro group. Where R ₄₆ is an aliphatic group,
Represents an aromatic group or a heterocyclic group, and represents R ₄₇ , R ₄₈ and R
₄₉ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. The meaning of the aliphatic group, the aromatic group or the heterocyclic group is the same as defined above.

K is an integer of 0 or 1;
Is preferably 0, that is, the case where Cp and X are directly bonded.

X is Cp- (T) _k by N, O or S
-Is a divalent linking group bonded to-, -O-, -S-,-
OCO-, -OCO (O)-, -OCO (S)-, -O
_{CONH -, - SO 2 -,} - OSO 2 NH- or N with Cp- (T) _k - and coupled to a Hajime Tamaki (such as pyrrolidine, piperidine, morpholine, piperazine, pyrrole,
Pyrazole, imidazole, 1,2,4-triazole, benzotriazole, succinimide, phthalimide, oxazolidine-2,4-dione, imidazolidin-2,4-dione, 1,2,4-triazolidine-3,
A group derived from 5-dione) or these groups and an alkylene group (eg, methylene, ethylene, propylene),
A cycloalkylene group (eg, 1,4-cyclohexylene), an arylene group (eg, o-phenylene, p-phenylene), a divalent heterocyclic group (eg, a group derived from pyridine, thiophene, or the like), —CO—, — SO ₂ -,-
COO -, - CONH -, - SO 2 NH -, - SO 2 O
-, - NHCO -, - NHSO 2 -, - NHCONH
_{-, - NHSO 2 NH -,} - NHCOO- linking group obtained by combining the like preferred.

X is more preferably represented by the following general formula (I). Formula (I) * -X _1- (L-X ₂ ) _m -** In formula (I), * represents a position bonding to Cp- (T) _k- , and ** represents a position bonding to Q. X ₁ is -O- or -S-, L is an alkylene group, X ₂ is -O-,-
S -, - CO -, - SO 2 -, - OCO -, - COO
-, - NHCO -, - CONH -, - SO 2 NH -, -
_{NHSO 2 -, - SO 2 O} -, - OSO 2 -, - OCO
(O)-, -OCONH-, -NHCOO-, -NHC
_{ONH -, - NHSO 2 NH -} , - OCO (S) -, -
SCO (O) -, - OSO 2 NH- or -NHSO ₂ O
And m represents an integer of 0 to 3.

The total number of carbon atoms of X (hereinafter referred to as C number) is preferably 0 to 12, more preferably 0 to 8. Most preferred is -OCH ₂ CH ₂ O- as X.

Q represents an arylene group or a divalent heterocyclic group. When Q is an arylene group, the arylene group may be a substituent (for example, a halogen atom, hydroxyl,
Carboxyl, sulfo, nitro, cyano, amino, ammonium, phosphono, phosphino, alkyl, cycloalkyl, aryl, carbonamide, sulfonamide,
Alkoxy, aryloxy, acyl, sulfonyl, carboxyl, carbamoyl, sulfamoyl), and the C number is preferably 6 to 15, more preferably 6 to 10. When Q is a divalent heterocyclic group, the heterocyclic group contains at least one heteroatom selected from N, O, S, P, Se or Te in the ring, and has 3 to 8 members, preferably 5 to 7 members. A monocyclic or condensed heterocyclic group such as pyridine, thiophene, furan, pyrrole, pyrazole,
Imidazole, thiazole, oxazole, benzothiazole, benzoxazole, benzofuran, benzothiophene, 1,3,4-thiadiazole, indole,
A group derived from quinoline or the like) and a substituent (Q
Is the same as the substituent in the case of an arylene group), the C number is preferably 2 to 15, more preferably 2 to
It is 10. Most preferred as Q are the following groups

[0210]

Embedded image

[0211]

Therefore, in the present invention, the most preferred
(T) _k -XQ- is a group shown below.

[0213]

Embedded image

[0214]

When R ₁₁ , R ₁₂ or R ₁₃ is an alkyl group, the alkyl group may be linear or branched, may contain an unsaturated bond, and may have a substituent (for example, halogen). Atom, hydroxyl, carboxyl, sulfo, phosphono, phosphine, cyano, alkoxy, aryl,
Alkoxycarbonyl, amino, ammonium, acyl, carbonamide, sulfonamide, carbamoyl,
(Sulfamoyl, sulfonyl).

When R ₁₁ , R ₁₂ or R ₁₃ is a cycloalkyl group, the cycloalkyl group may be a 3- to 8-membered cycloalkyl group having an unsaturated bond even if it has a crosslinking group. May have a substituent (same as the substituent when R ₁₁ , R ₁₂ or R ₁₃ is an alkyl group).

When R ₁₁ , R ₁₂ or R ₁₃ is an aryl group, the aryl group may have a substituent (R ₁₁ ,
In addition to the substituent when R ₁₂ or R ₁₃ is an alkyl group, examples include alkyl and cycloalkyl. ) May be included.

When R ₁₁ , R ₁₂ or R ₁₃ is a heterocyclic group, the heterocyclic group has at least one of N, S, O, R, and Se.
Or 3 to 8 containing a hetero atom selected from Te in the ring.
Membered (preferably 5 to 7 membered) monocyclic or condensed ring heterocyclic group (for example, imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl), wherein the substituent (R ₁₁ , R ₁₂ or R ₁₃ is aryl) The same as the substituent in the case of a group).

[0219] Here a carboxyl group is a carboxylate group, a sulfo group sulfonate group, a phosphino group phosphinate group, a phosphono group may include each phosphonate group, this time counterion example Li ^+, Na
⁺ , K ⁺ , and ammonium.

R ₁₁ is preferably a hydrogen atom, a carboxyl group, or an alkyl group having 1 to 10 carbon atoms (eg, methyl, t-butyl, sulfomethyl, 2-sulfoethyl, carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl,
Benzyl, ethyl, isopropyl) or 6-12 C atoms
(For example, phenyl, 4-methoxyphenyl, 4-sulfophenyl), particularly preferably a hydrogen atom, a methyl group or a carboxyl group.

R ₁₂ is preferably a cyano group, a carboxyl group, a carbamoyl group having 1 to 10 carbon atoms, a sulfamoyl group having 0 to 10 carbon atoms, a sulfo group, an alkyl group having 1 to 10 carbon atoms (eg, methyl, sulfomethyl), A C 1-10 sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), a C 1-10 carbonamide group (eg, acetamido, benzamide) or a C 1-10 sulfonamide group (eg, methanesulfonamide, toluenesulfone Amide), and particularly preferably a cyano group, a carbamoyl group or a carboxyl group.

R ₁₃ is preferably a hydrogen atom, and has 1 to 12 carbon atoms.
(E.g., methyl, sulfomethyl, carboxymethyl, 2-sulfoethyl, 2-carboxyethyl,
Ethyl, n-butyl, benzyl, 4-sulfobenzyl)
Or an aryl group having 6 to 15 C atoms (for example, phenyl, 4
-Carboxyphenyl, 3-carboxyphenyl, 4-
Methoxyphenyl, 2,4-dicarboxyphenyl, 2
-Sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 2,5-disulfophenyl), more preferably an alkyl group having 1 to 7 carbon atoms or 6 to 10 carbon atoms. Is an aryl group.

R ₁₄ is specifically an acyl group represented by the general formula (II) or a sulfonyl group represented by the general formula (III). General formula (II) R ₃₁ CO— General formula (III) When R ₃₁ SO ₂ —R ₃₁ is an alkyl group, the alkyl group may have a straight or branched chain, including an unsaturated bond. Substituents (e.g., halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino,
Ammonium, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).

When R ₃₁ is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group and may have a substituent even if it has a crosslinking group or an unsaturated bond. Group (same as the substituent when R ₃₁ is an alkyl group)
May be provided.

When R ₃₁ is an aryl group, the aryl group, even if it is a condensed ring, has a substituent (in addition to the substituent when R ₃₁ is an alkyl group, alkyl, cycloalkyl, etc.). You may.

When R ₃₁ is a heterocyclic group, the heterocyclic group has at least one hetero atom selected from N, S, O, P, Se or Te in the ring and has 3 to 8 members (preferably 5
Monocyclic Hajime Tamaki or a condensed 7-membered) (e.g. imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, a quinolinyl), have the same) in a substituent when the substituent (R ₃₁ is an aryl group It may be.

[0227] Here a carboxyl group is a carboxylate group, a sulfo group sulfonate group, a phosphino group phosphinate group, a phosphono group may include each phosphonate group, this time counterion example Li ^+, Na
⁺ , K ⁺ , and ammonium.

R ₃₁ is preferably an alkyl group having 1 to 10 carbon atoms (eg, methyl, carboxymethyl, sulfoethyl, cyanoethyl), a cycloalkyl group having 5 to 8 carbon atoms (eg, cyclohexyl, 2-carboxycyclohexyl), or An aryl group having a number of 6 to 10 (for example, phenyl, 1-naphthyl, 4-sulfophenyl), particularly preferably an alkyl group having 1 to 3 carbon atoms and an aryl group having 6 carbon atoms.

R ₁₅ is a substitutable group, preferably an electron donating group, particularly preferably —NR ₃₂ R ₃₃ or —OR ₃₄ . The substitution position is preferably the 4-position. R ₃₂ , R ₃₃ and R ₃₄ are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and are the same as R ₃₁ . A ring may be formed between R ₃₂ and R ₃₃ , and the nitrogen hetero ring formed is preferably an alicyclic ring.

J represents an integer of 0 to 3, preferably 1 or 2, and particularly preferably 1.

When R ₁₆ or R ₁₇ is an alkyl group, the alkyl group may be linear or branched, may contain an unsaturated bond, and may have a substituent (for example, a halogen atom, hydroxyl, Carboxyl, sulfo, phosphono,
Phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).

When R ₁₆ or R ₁₇ is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group which has a crosslinking group and an unsaturated bond. May have a substituent (the same as the substituent when R ₁₆ or R ₁₇ is an alkyl group).

When R ₁₆ or R ₁₇ is an aryl group,
Even if the aryl group is a condensed ring, the substituent (R ₁₆ or R _16
In addition to the substituent when ₁₇ is an alkyl group, there are alkyl, cycloalkyl, and the like).

When R ₁₆ or R ₁₇ is a heterocyclic group, the heterocyclic group contains at least one heteroatom selected from N, S, O, P, Se or Te in the ring and is a 3- to 5-membered member. (Preferably 5 to 7 members) a monocyclic or condensed heterocyclic group (for example, imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl), and a substituent (R ₁₆
Or the same as the substituent when R ₁₇ is an aryl group).

[0235] Here a carboxyl group is a carboxylate group, a sulfo group sulfonate group, a phosphino group phosphinate group, a phosphono group may include each phosphonate group, this time counterion example Li ^+, Na
⁺ , K ⁺ , ammonium and the like.

R ₁₆ is preferably a cyano group, a carboxyl group, a carbamoyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 11 carbon atoms, or a 0 to 10 carbon atoms. Sulfamoyl group, sulfo group, alkyl group having 1 to 10 carbon atoms (eg, methyl, carboxymethyl, sulfomethyl), sulfonyl group having 1 to 10 carbon atoms (eg, methylsulfonyl, phenylsulfonyl), carbonamide group having 1 to 10 carbon atoms (Eg, acetamide, benzamide), a C1-10 sulfonamide group (eg, methanesulfonamide, toluenesulfonamide), an alkyloxy group (eg, methoxy, ethoxy) or an aryloxy group (eg, phenoxy), and particularly preferably. Cyano group, carbamoyl group, alkoxycarbonyl group, It is a carboxyl group.

R ₁₇ is preferably a hydrogen atom, and has 1 to 1 C atoms.
Alkyl groups such as methyl, sulfomethyl, carboxymethyl, ethyl, 2-sulfoethyl, 2-carboxyethyl, 3-sulfopropyl, 3-carboxypropyl, 5-sulfopentyl, 5-carboxypentyl,
-Sulfobenzyl) or an aryl group having 6 to 15 C atoms (for example, phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 2,4-dicarboxyphenyl, 4-
Sulfophenyl, 3-sulfophenyl, 2,5-disulfophenyl, 2,4-disulfophenyl), more preferably an alkyl group having 1 to 7 carbon atoms or 6 to 10 carbon atoms.
Is an aryl group.

Hereinafter, specific examples of the yellow colored cyan coupler of the present invention will be shown, but the present invention is not limited thereto.

[0239]

Embedded image

[0240]

Embedded image

[0241]

Embedded image

[0242]

Embedded image

[0243]

Embedded image

[0244]

Embedded image

[0245]

Embedded image

[0246]

Embedded image

[0247]

Embedded image

[0248]

Embedded image

The yellow colored coupler represented by the general formula (CI) of the present invention is generally synthesized by a diazo coupling reaction between a 6-hydroxy-2-pyridone and an aromatic diazonium salt or a heterocyclic group diazonium salt having a coupler structure. can do.

The former, that is, 6-hydroxy-2-pyridones are described in Kleinsberg, "Heterocyclic Compounds-Pyridines and Derivatives-Part 3" (Interscience Publishing, 1962), Journal of the American Chemical.・ Society (J.Am. Chem. Soc.) 194
3 years, 65, 449, Journal of the Chemical Technology and Biotechnology (J. C.
hem. Tech. Biotechnol.) 1986, 36, 410
Page, Tetrahedron 1966, 22
Vol. 445, Japanese Patent Publication No. 61-52827, West German Patent Nos. 2,162,612, 2,349,709 and 2,902,486, and U.S. Pat. No. 3,763,170.
Can be synthesized by the method described in No.

The latter diazonium salt is disclosed in US Pat.
04,929 and 4,138,258, JP-A-61-61
-72244, 61-273543 and the like. 6-hydroxy-2-
The diazo coupling reaction between the pyridone and the diazonium salt is carried out in a solvent such as methanol, ethanol, methyl cellosolve, acetic acid, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane, water or a mixed solvent thereof. Can do it. At this time, for example, sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, pyridine, triethylamine, tetramethylurea, and tetramethylguanidine can be used as the base. The reaction temperature is usually
The temperature is from 78 ° C to 60 ° C, preferably from -20 ° C to 30 ° C.

The synthesis route of the yellow colored cyan coupler of the present invention is shown below.

[0253]

Embedded image

[0254]

Embedded image

[0255]

Embedded image

[0256]

Embedded image

[0257]

Embedded image

The yellow colored cyan couplers represented by formulas (CII) to (CIV) are described in JP-B-58-6939.
The couplers can be synthesized by the methods described in the above-mentioned patents and the like as a method for synthesizing a coupler represented by JP-A No. 1-197563 and the general formula (CI).

In the present invention, yellow colored cyan couplers represented by formulas (CI) and (CII) are more preferably used. Those represented by the general formula (CI) are particularly preferably used.

The yellow colored cyan coupler of the present invention is preferably added to a light-sensitive silver halide emulsion layer or a layer adjacent thereto in a light-sensitive material, and particularly preferably to a red light-sensitive emulsion layer. The total amount of the photosensitive material is a 0.005~0.30g / m ^2, preferably 0.02~0.20g / m ^2, more preferably 0.03
０．１0.15 g / m ² .

As for the method of adding the yellow colored cyan coupler of the present invention, it can be added in the same manner as in the ordinary coupler as described later.

The silver halide grains used in the present invention include silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
It is silver chloroiodobromide. Other silver salts, such as rodin silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. In order to appropriately suppress development, the emulsion preferably contains silver iodide. In the case of the emulsion of the present invention, it is a silver halide containing 1 to 30 mol% of silver iodide, preferably 1.5 to 1.5 mol%. To 15 mol%, particularly preferably 2 to 10 mol%.

In the present invention, the average iodine content of the silver halide grains in the red-sensitive layer and / or the green-sensitive layer is preferably from 2 to 5 mol%, more preferably from 3 to 4 mol%.
Is more preferable. The average iodine content of the silver halide grains in the all red-sensitive layer is defined as 100 by dividing the total iodine molar amount (I) by the total silver halide molar amount (AgX) present in the all red-sensitive emulsion layer. Multiplied value. In the present invention, at least one emulsion layer of the red-sensitive layer and the green-sensitive layer preferably has an average silver iodide content of 6 mol% or less.

In the present invention, it is necessary that at least one red, green, and blue-sensitive silver halide emulsion layer is present, but it is preferable that at least two layers each have a different sensitivity. The red-sensitive layer is preferably composed of three layers having different sensitivities. The silver halide grains used in the present invention may be normal crystals containing no twin planes or multiple twins having twin planes. In the case of a normal crystal, a cube having a (100) plane, an octahedron having a (111) plane, and Japanese Patent Publication No. 55-427.
No. 37 and dodecahedral particles having a (110) plane disclosed in JP-A-60-222842 can be used. Furthermore, the (100) plane and the (111) plane coexist.
Face particles can also be used.

In the red-sensitive layer and / or the green-sensitive layer of the present invention, particularly, the highest sensitivity layer, the following tabular grains are preferably used.

In the present invention, tabular silver halide grains (hereinafter, referred to as tabular grains) are a general term for grains having one twin plane or two or more parallel twin planes. In this case, the twin plane refers to the (111) plane when ions at all lattice points have a mirror image relationship on the (111) plane side. The tabular grains have a triangular, hexagonal or rounded circular shape when the grains are viewed from above, and triangular grains are triangular, hexagonal grains are hexagonal, and circular. Shaped ones have circular outer surfaces parallel to each other.

In the present invention, the aspect ratio of at least 50% of the total projected area of the silver halide grains is preferably 3 or more. More preferably, 75% or more is 3 or more for the present invention. In addition, the aspect ratio of the tabular grains in the present invention is a value obtained by dividing each grain diameter by the thickness of the tabular grains having a diameter equivalent to a circle having a projected area of 0.1 μm or more.
The measurement of the particle thickness is performed by evaporating a metal from the diagonal direction of the particles together with the reference latex, measuring the shadow length on an electron micrograph, and calculating by referring to the shadow length of the latex. Easy. The particle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle. The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the projection magnification. In the present invention, the tabular grains preferably have a diameter of 0.15 to 5.0 μm. The thickness of the tabular grains is 0.05 to 1.0 μm
It is preferred that In the present invention, the size distribution of the tabular grains may be polydisperse, but is preferably monodisperse (the coefficient of variation defined by the following formula is within 25%). Coefficient of variation = (standard deviation of particle size / average particle size)
× 100 The tabular grains in the present invention are silver iodobromide and silver iodochlorobromide containing 1.5 mol% or more, preferably 2 mol% or more and 6 mol% or less of iodine.

The tabular grains may have at least two layered structures having substantially different iodine compositions or chlor compositions in the silver halide grains, or may have a uniform composition. For example, emulsions having a layered structure with different iodine compositions include those containing a high iodine layer in the core and a low iodine layer in the outermost layer, and those containing a low iodine layer in the core and a high iodine layer in the outermost layer. You may. Further, the layered structure may be composed of three or more layers.

The tabular grains in the present invention can be prepared by the following precipitation method. That is, a dispersion medium is put into a commonly used reactor for forming a silver halide precipitate having a stirring mechanism. Usually, the amount of dispersion medium which is introduced into the reactor in the first stage is at least about 10%, preferably 20%, of the amount of dispersion medium present in the emulsion during the precipitation stage of the final grains.
~ 80%. The dispersion medium to be initially introduced into the reactor is water or a dispersion medium of a deflocculant in water. This dispersion medium may contain, if necessary, other components such as one or more halogens. A silver halide ripening agent and / or a metal dopant described later is blended. The peptizer can also be initially present in the reaction solution, in which case the concentration is at least 10%, in particular at least 20%, of the total amount of peptizer present in the final stage of silver halide precipitation formation. preferable. Additional dispersion medium is added into the reactor along with silver and halide salts, which can be introduced from another jet. Generally, the proportion of the dispersion medium is adjusted after the halide salt introduction has been completed, especially in order to increase the proportion of the deflocculant.

Also, usually less than 10% by weight of the bromide salt used for the production of silver halide grains is initially present in the reactor to control the concentration of bromide ion in the dispersion medium at the start of silver halide precipitation. I do. Here, the dispersion medium in the reactor initially contains substantially no iodide ions. This is because, if iodine ions are present before silver, bromide salt and chloride salt are added simultaneously, thick non-tabular grains are likely to be formed. Here, “substantially free of iodine ion” means that the iodide ion is a separate and independent silver iodide phase (β-
(AgI or γ-AgI) means that they are present in insufficient amounts to precipitate. It is desirable to maintain the iodine concentration in the reactor before introducing the silver salt at less than 0.5 mol% of the total halide ion concentration in the reactor. If the pBr of the dispersion medium is initially too high, the tabular grains produced will be relatively thick and the grain thickness distribution will be broad. Further, non-tabular grains increase. On the other hand, p
If the Br is too low, non-tabular grains are also likely to be formed.
Here, pBr is defined as a negative value of the logarithm of the bromide ion concentration.

During the formation of the precipitate, silver, bromide, chloride and iodo salts are added to the reactor according to techniques well known for the formation of silver halide grains. Usually, an aqueous solution of a soluble silver salt such as silver nitrate is introduced into the reactor simultaneously with the introduction of the bromide, chloride and iodide salts. Also, the bromide, chloride and iodide salts are introduced as an aqueous salt solution, such as an aqueous solution of a soluble ammonium, alkali metal (eg, sodium or potassium) or alkaline earth metal (eg, magnesium or calcium) halide salt. The silver salt is at least initially introduced into the reactor separately from the bromide, chloride and iodine salts. The bromide, chloride and iodine salts may be added separately or introduced as a mixture.

The introduction of the silver salt into the reactor initiates the grain nucleation stage. Continued introduction of silver, bromide, chloride and iodide salts forms a population of silver bromide, silver chloride and grain nuclei that serve as precipitation sites for silver iodide. The grains enter the growth phase due to the precipitation of silver bromide, silver chloride and silver iodide on existing grain nuclei. The conditions for nucleation can be referred to the method described in JP-A-63-11928, but the method is not limited to this method. For example, the nucleation temperature is in the range of 5 to 55 ° C. Can be.

The size distribution of the tabular grains formed in the present invention is greatly affected by the concentrations of bromide, chloride and iodine salts in the growth stage. That is, when pBr is too low, tabular grains having a high aspect ratio are formed,
The coefficient of variation of the projected area becomes extremely large. By maintaining pBr between about 2.2 and 5, tabular grains having a small coefficient of variation of projected area can be formed.

Provided that the above-mentioned pBr conditions are satisfied, the concentrations and introduction rates of silver, bromide, chloride and iodide salts may be the same as those conventionally used. It is desirable to introduce the silver and halide salts at a concentration of 0.1 to 5 molar per liter. However, a wider range of concentrations conventionally used conventionally, for example, from 0.01 moles per liter to saturation, can be employed. A particularly preferred precipitation method is to increase the rate of introduction of the silver and halide salts to reduce the precipitation time. The rate of introduction of the silver and halide salts can be increased by increasing the rate of introduction of the dispersion medium and the silver and halide salts, or by increasing the concentration of the silver and halide salts in the introduced dispersion medium. . By keeping the addition rates of silver and halide salts close to the limit at which the generation of new grain nuclei occurs as described in JP-A-55-142329, the variation coefficient of the projected area of grains can be further reduced. . The amount of gelatin in the reactor during the nucleation has a significant effect on the particle size distribution. The gelatin concentration is preferably 0.5 to 10% by weight, more preferably 0.5 to 10% by weight.
6 wt% is preferred. In addition, the stirring rotation speed and the shape of the reactor also affect the distribution of the formed particle size.

In the present invention, as a stirring and mixing apparatus used for forming tabular grains, US Pat.
As described in No. 7, a device for adding and mixing the reaction solution into the solution is preferable, and the set stirring speed may not be too low or too high. When the stirring rotation speed is low, the generation ratio of non-parallel twin grains increases, and when it is too high, the generation frequency of tabular grains decreases, and the size distribution also widens. The shape of the reactor used for forming the tabular grains is most preferably a bottom having a semicircular shape.

The tabular silver halide grains in the present invention preferably have dislocation lines. Dislocations in tabular grains are described, for example, in J, F. Hamilton, Phot. Sci. Eng., 11, 5
7, (1967) and T. Shiozawa, J. Soc. Phot. Sci. Japa
n, 35, 213, (1972) can be observed by a direct method using a transmission electron microscope at a low temperature.
That is, first, silver halide grains are taken out of the emulsion without applying a pressure at which dislocations can be generated. Next, the particles are placed on a mesh for observation with an electron microscope, and observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (for example, printout) by an electron beam. In this case, the larger the thickness of the particles, the more difficult it is for an electron beam to pass therethrough.
(0 kV or more) can be observed more clearly by using an electron microscope. In the present invention, the number of tabular grains having dislocation lines is preferably at least 50%, more preferably at least 70%, of the total number of tabular grains.

The dislocation lines are, for example, in tabular grains,
It can be introduced near the outer periphery. In this case, the dislocation is substantially perpendicular to the outer periphery of the grain, and the dislocation line is generated in a region starting from the position of x% of the distance from the center of the tabular grain to the side (outer periphery) and reaching the outer periphery. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape of the region formed by connecting the dislocation start positions is close to the shape similar to the particle shape, but may be a distorted shape instead of a perfect similar shape. The dislocations forming this distorted figure are not seen in the central region of the grain. The direction of the dislocation lines is about (211) crystallographically, but they are often meandering and sometimes intersect each other.

In the present invention, the tabular grains may have dislocation lines almost uniformly over the entire outer periphery thereof, or may have dislocation lines localized on the outer periphery.
That is, in the case of hexagonal tabular silver halide grains as an example, dislocation lines may exist only in the vicinity of the six vertices, and dislocation lines may be localized only in the vicinity of one of the six vertices. Conversely, dislocation lines can be present only on each side of the hexagon except for the vicinity of the six vertices.

Further, the dislocation lines may be formed over a region including the centers of two parallel main surfaces of the tabular grains. When dislocation lines are formed over the entire main surface, the direction of the dislocation lines is approximately (211), (110), or a random direction when viewed from a direction perpendicular to the main surface. There may be. Further, the length of each dislocation line is also random, and when it is observed as a short line on the main surface, it may be observed as a long line reaching the outer periphery of the main surface. When the dislocation lines are straight, they may meander, and often intersect each other.

In the tabular grains, the dislocations may be introduced at any of the outer periphery, the main surface, and the local position of the grains as described above, or a combination thereof. That is, dislocations may be present on the outer periphery and on the main surface at the same time. The dislocation in the tabular grains of the present invention can be controlled by providing a specific phase having a high silver iodide content inside the grains. Specifically, a substrate grain is prepared, and the grain is provided with an internal high iodine phase by the following method 1), 2) or 3). Coating with a low-percentage phase allows for control of dislocations within the grains.

The silver iodide content of the tabular grains serving as the substrate grains is lower than that of the internal high iodine phase, preferably from 0 to 0%.
It is 12 mol%, more preferably 0 to 10 mol%.

The internal high iodine phase means a silver halide solid solution containing silver iodide at a relatively high content. In this case, the silver halide is preferably silver iodide, silver iodobromide, or silver chloroiodobromide emulsion, more preferably silver iodide or silver iodobromide (silver iodide content: 10 to 40 mol%). Preferably, silver iodide is particularly preferred.

The internal high iodine phase is not uniformly deposited on the plane of the tabular grains of the substrate, but rather it is important that it be present locally. Such a localized location of the high iodine phase may be any site on the main surface, side surface, side, or corner of the tabular grains. Furthermore, the internal high iodine phase may be selectively epitaxially coordinated at a site as described above.

The following are methods 1) to 3) for forming a high iodine phase.
Will be described.

1) For example, E. Klein, E. Moisar, G. Mu
A so-called conversion method as described in rch, Phot. Xorr., 102 (4), 59-63 (1966). In this method, for example, during the grain formation, halogen ions having a lower solubility of a salt providing silver ions than halogen ions forming the grains (or near the surface of the grains) at that time are used. There is a method of adding. In the present invention, it is preferable that the amount of halogen ions having a low solubility to be added is not less than a certain value (related to the halogen composition) with respect to the unit surface area of the particles at that time. For example,
During the particle formation, it is preferable to add a certain amount or more of the KI amount to the surface area of the AgBr particles at that time. Specifically, K of 8.2 × 10 ⁻⁵ mol / m ² or more
It is preferred to add I.

2) For example, see JP-A-59-133540
Nos. 58-108526 and 59-162540. In this method, a substance that locally controls epitaxial growth, such as an adsorptive spectral sensitizing dye, can be used. These substances are added or the conditions for particle growth (eg, pAg, p
H, temperature) and adding a halide solution containing a silver salt and iodine can form an internal high iodine phase.

3) Alternatively, an internal high iodine phase can be formed by adding fine silver iodide grains during tabular grain formation. The equivalent spherical diameter of the fine silver iodide grains used in this method is 0.3 μm or less, more preferably 0.1 μm or less.

In the present invention, the outer phase covering the high iodine phase has a lower silver iodide content than the high iodine phase, preferably 0 to 12 mol%, more preferably 0 to 1 mol%.
0 mol%, most preferably 0-3 mol%.

In the process of forming tabular silver halide grains or physical ripening, for example, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof may be added to the silver halide emulsion constituting the light-sensitive material of the present invention. A rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may coexist as a metal dopant.

The addition amount of the sensitizing dye used in the light-sensitive material of the present invention is preferably 40% or more of the saturated adsorption amount, more preferably 40 to 120%, further preferably 70% to 100%. is there. The saturated adsorption amount of the sensitizing dye can be determined from the adsorption isotherm by centrifuging the emulsion on which the dye is adsorbed. The sensitizing dye may be added during the formation of silver halide grains or during the chemical sensitization, or may be added during coating. In particular, as for the method of adding a sensitizing dye during the formation of silver halide emulsion grains, refer to U.S. Pat. Nos. 4,225,666 and 4,828,972 and JP-A-61-103,149. be able to. As a method of adding a sensitizing dye in a desalting step of a silver halide emulsion, EP 291 339-
No. A, JP-A-64-52,137 can be referred to. The method of adding a sensitizing dye in the chemical sensitization step can be referred to JP-A-59-48,756.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostil compounds substituted with a nitrogen-containing heterocyclic group (for example, US Pat. No. 2,933,390,
No. 3,636,721), and aromatic organic acid formaldehyde condensates (for example, US Pat.
3,510), cadmium salts, azaindene compounds and the like. US Patent 3,615,
No. 613, No. 3,615,641, No. 3,617,2
The combinations described in Nos. 95 and 3,635,721 are particularly useful.

The silver halide emulsion is usually chemically sensitized. For chemical sensitization, for example, H.I. Freesel (H.
Frieser, ed., Die Grundlagen derPhotographischen Prozess
emit Silberhalogeniden (Academiache Ferragus Gesellshaft 1968), pages 675 to 734. That is, in the present invention, a silver halide emulsion contains, for example, a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate,
Sulfur sensitization method using thioureas, mercapto compounds, rhodanines); reduction sensitization method using reducing substances (for example, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); A noble metal sensitization method using a noble metal compound (for example, a gold complex salt, or a complex salt of a metal of the Periodic Table VIII such as Pt, Ir, or Pd); a selenium compound (for example, selenoureas, selenoketones,
Chemical sensitization can be performed by a selenium sensitization method using a selenide. In particular, in the present invention, the tabular silver halide grains are chemically sensitized with at least one of a selenium sensitizer, a gold sensitizer, and a sulfur sensitizer.

As the selenium sensitizer, selenium compounds disclosed in known publications can be used. That is,
An unstable selenium compound and / or a non-unstable selenium compound are added to the silver halide emulsion containing the tabular silver halide grains, and the mixture is stirred at a high temperature, preferably at 40 ° C. or higher for a certain time. Examples of the unstable selenium compound include, for example, JP-B-44-15748 and JP-B-43-43.
No. 13489, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2
No. 229300 may be used. Specific examples of the unstable selenium compound include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, 2 -Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (for example, bis (3-
Chloro-2,6-dimethoxybenzoyl) selenide),
Selenophosphates, phosphine selenides, colloidal metal selenium are mentioned.

However, in the present invention, the unstable selenium compound is not particularly limited to the compounds described above. It is understood by those skilled in the art that the structure of an unstable selenium compound as a sensitizer of a photographic emulsion is not important if selenium is unstable, and the organic portion in the selenium sensitizer molecule supports selenium. It is generally understood that it has no function other than to make it exist in the emulsion in an unstable form. In the present invention, various unstable selenium compounds can be used based on such a broad concept.

The non-labile selenium compounds include, for example, JP-B-46-4553 and JP-B-52-3.
No. 4,492, JP-B-52-34491 can be used. Specific examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, and 2-selenazo. Lysinedione, 2-selenooxazolidinethione, and derivatives thereof.

Of the above selenium compounds, a compound of the following general formula (I) and a compound of the general formula (II) are preferable.

[0297]

Embedded image

In the formula, Z ³ and Z ⁴ may be the same or different and each represents an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl) , Propenyl), an aralkyl group (eg, benzyl, phenethyl), an aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), a heterocyclic group (Eg, pyridyl, thienyl, furyl, imidazolyl),-
NR ³ (R ^4), - represents a OR ⁵ or -SR ^6. R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different and each represents an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. These alkyl group, an aralkyl group, an aryl group, and specific examples of the heterocyclic group include the same groups as in the case of Z ³ described above. In addition, R ³ and R ⁴ are a hydrogen atom or an acyl group (eg, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl) It may be.

In the general formula (I), preferably, Z ³ represents an alkyl group, an aryl group, or —NR ³ (R ⁴ ), and Z ⁴ represents —NR ⁷ (R ⁸ ). However, R ³ , R ⁴ ,
R ⁷ and R ⁸ may be the same or different,
Represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.

The general formula (I) is more preferably
N, N-dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoaminode, N-alkyl-N-aryl-arylseleno Represents an amide.

[0301]

Embedded image

In the formula, Z ⁵ , Z ⁶ , and Z ⁷ may be the same or different, and each represents an aliphatic group, an aromatic group,
Heterocyclic ^{group, -OR 9, -OR 10 (R} 11), - SR 12, -
SeR ¹³ , X, represents a hydrogen atom. R ⁹ , R ¹² and R ¹³ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom,
Or a cation, wherein R ¹⁰ and R ¹¹ represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom, and X represents a halogen atom.

In the general formula (II), Z ⁵ , Z ⁶ , Z
^{As the} aliphatic group represented by ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ , a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl, Ethyl, n-propyl, isopropyl, t-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl,
2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl). In the general formula (II), Z ⁵ , Z ⁶ , Z ⁷ , R ⁹ , R ¹⁰ , R
^{As the} aromatic group represented by ¹¹ , R ¹² and R ¹³ , a monocyclic or condensed aryl group (for example, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-methyl Phenyl). In the general formula (II), Z ⁵ , Z ⁶ , Z ⁷ , R ⁹ ,
As the heterocyclic group represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ , a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom and an oxygen atom (for example, , Pyridyl, thienyl, furyl, thiazolyl, imidazolyl, benzimidazolyl).

In the general formula (II), R ⁹ , R ¹² ,
And cations represented by R ¹³ include alkali metal atoms and ammonium; and halogen atoms represented by X include fluorine, chlorine, bromine and iodine.

In the general formula (II), preferably, Z ⁵ ,
Z ⁶ and Z ⁷ are an aliphatic group, an aromatic group, or —OR
Represents ^9, R ⁹ represents an aliphatic group or an aromatic group.

The formula (II) more preferably represents a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate, or a triarylselenophosphate.

Specific examples 1 to 40 of the selenium compounds represented by formulas (I) and (II) are listed, but the selenium sensitizer used in the present invention is not limited to these.

[0308]

Embedded image

[0309]

Embedded image

[0310]

Embedded image

[0311]

Embedded image

[0312]

Embedded image

The selenium sensitizer described above is dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, and added to the silver halide emulsion during chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more selenium compounds may be used in combination. It is preferable to use the unstable selenium compound and the non-unstable selenium compound together.

The addition amount of the selenium sensitizer used in the present invention varies depending on, for example, the activity of the selenium sensitizer used, the type of silver halide and the size of grains, the ripening temperature and time, but is preferably used. Is 1 × 1 per mole of silver halide
It is from 0 ^-7 mol to 5 × 10 ^-5 mol. In the present invention, the temperature of chemical sensitization when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or more and 80 ° C. or less. The pAg and pH are arbitrary, and for example, the effect of selenium sensitization can be obtained in a wide range of pH 4 to 9.

In the present invention, the selenium sensitization is more preferably performed in the presence of a silver halide solvent.

Examples of the silver halide solvent usable in the present invention include, for example, US Pat. Nos. 3,271,157, 3,531,289, 3,574,628,
(A) Organic thioethers described in JP-A-54-1019 and JP-A-54-158917;
No. 82408, No. 55-77737, No. 55-298
No. 2 (b) Thiourea derivative, JP-A-53-14
No. 4319, (c) a silver halide solvent having a thiocarbonyl group interposed between an oxygen or sulfur atom and a nitrogen atom, (d) imidazoles described in JP-A-54-100717, and (e) sulfurous acid And (f) thiocyanate.

Particularly preferred silver halide solvents include:
Thiocyanates and tetramethylthioureas are mentioned. The amount of the solvent used varies depending on the kind. For example, in the case of thiocyanate, the preferred amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² or less per mol of silver halide.

In the silver halide emulsion containing tabular grains in the light-sensitive material of the present invention, sulfur sensitization and gold sensitization may be used together in the chemical sensitization. Sulfur sensitization
Usually, a sulfur sensitizer is added to the emulsion, and the emulsion is stirred at a high temperature, preferably at 40 ° C. or higher for a certain time. The gold sensitization is usually performed by adding a gold sensitizer to the emulsion and stirring the mixture at a high temperature, preferably at 40 ° C. or higher for a certain period of time.

In the sulfur sensitization, a compound known as a sulfur sensitizer can be used. Specifically, for example, allyl thiocarbamide thiourea, allyl isothiocyanate,
Cystine, p-toluenethiosulfonate, rhodanine. In addition, US Pat. No. 1,574,944
No. 2,410,689 and No. 2,278,94
No. 7, No. 2,728,668, No. 3,501,3
No. 13, No. 3,656,955, German Patent 1,4
22,869, JP-B-56-24937, and JP-A-5
The sulfur sensitizers described in JP-A-5-45016 can be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the silver halide emulsion. This amount can vary over a wide range under various conditions such as pH, temperature, and size of silver halide grains, but is at least 1 × 10 ⁻⁷ mol and 5 × 10 ⁻ mol per mol of silver halide. ^It is preferably at most ⁵ mol.

The gold sensitizer used for the gold sensitization may have a gold oxidation number of +1 or +3, and gold compounds commonly used as gold sensitizers may be used. Representative examples thereof include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, and pyridyl trichlorogold. The amount of the gold sensitizer varies depending on various conditions, but is generally 1 × 10 ⁻⁷ mol or more per mol of silver halide.
It is preferably at most ^10-5 mol.

In the present invention, the timing and order of addition of the silver halide solvent, selenium sensitizer, sulfur sensitizer, and gold sensitizer during chemical ripening are not particularly limited. For example, the compounds may be added at the same time or at different times, preferably at the beginning of chemical ripening or during the progress of chemical ripening. The compound may be added by dissolving the compound in water or an organic solvent miscible with water, for example, a single solution or a mixture of methanol, ethanol, and acetone.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. . That is, azoles,
For example, benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenz Imidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly, 1-phenyl-
5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinethione; azaindenes such as tetraazaindenes (particularly, Many compounds known as antifoggants or stabilizers, such as 4-hydroxy-substituted (1,3,3a, 7) tetraazaidenes); benzenethiosulfonic acids; benzenesulfinic acid; The timing of addition of these antifoggants or stabilizers is usually after chemical sensitization, but can be more preferably selected during chemical ripening or before chemical ripening. That is, in the course of silver halide emulsion grain formation, during the addition of the silver salt solution or during the period from the addition to the start of chemical ripening, during chemical ripening (during the chemical ripening time, preferably within 50% from the start). , More preferably within a time period of up to 20%).
The amount of the compound to be used in the present invention cannot be univocally determined by the method of addition or the amount of silver halide.
^{The amount is from -7} mol to 10 ^-2 mol, more preferably from 10 ^-5 to 10 ^-2 mol.

As the preservative (binder or protective colloid) used in the photographic emulsion of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. Examples of the hydrophilic colloid include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sodium alginate and starch. Sugar derivatives such as derivatives; for example, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
Various kinds of synthetic hydrophilic high molecular substances such as a single or copolymer such as polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used. Examples of the gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Phot. Japan,
No. 16, page 30 (1966), an enzyme-treated gelatin may be used, and a hydrolyzate or an enzyme-decomposed product of gelatin can also be used. Examples of the gelatin derivative include various types of gelatin such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds. What is obtained by reacting the compound of the above is used.

[0324] The dispersion medium used in the present invention is, specifically, RESEARCH DISCLOSURE,
Volume 176, No. 17643 (December 1978)
Month) in section IX.

The light-sensitive material of the present invention can be used for a color photographic light-sensitive material. The light-sensitive material may be provided with at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. There is no particular limitation on the number and order of the non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, even if the above installation order is reversed according to the purpose,
Also, the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A-61-43748,
59-113438, 59-113440, 61-20037, 61-200
It may contain a coupler, a DIR compound or the like as described in JP-B-38, and may contain a color mixing inhibitor as usually used. The plurality of silver halide emulsion layers constituting each unit photosensitive layer preferably employ a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer as described in German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, JP-A-62-200350, JP-A-62-206541, JP-A-62-206541
As described in JP-A-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH. Also Tokunoaki
As described in JP-A-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the layers can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. As described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in the same color-sensitive layer from the side remote from the support. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. The arrangement may be changed as described above even in the case of four or more layers. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The tabular grains preferably used in the red-sensitive layer and / or the green-sensitive layer, particularly preferably used in the highest-speed layer, have been described above. Regarding the silver halide used in combination with these layers or used in other light-sensitive layers, It is described below. The grain size of the silver halide used in the present invention is about 0.2 μm
The following fine particles or large-sized particles having a projected area diameter of up to about 10 μm may be used, and a polydisperse emulsion or a monodisperse emulsion may be used. The silver halide photographic emulsion usable in the present invention is described, for example, in Research Disclosure (RD) No. 17643 (19).
December 1978), pp. 22-23, "I. Emulsion prepa
ration and types) ”and No. 18716 (November 1979),
648 pages, No. 307105 (November 1989), pp. 863-865, and "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Chimie et Physique Photographiqu
e, Paul Montel, 1967), Duffin, Photographic Emulsion Chemistry, Focal Press (GF Duffin, Photogra
phic Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions", by Zerikman et al., Focal Press (VL Zelikman et al., Making and Coating).
Photographic Emulsion, Focal Press, 1964).

In addition, as the emulsion used in the present invention, monodispersed emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gatoff, Photographic Science and Engineering (Gutoff, Photographic Science and Engin).
eering), Vol. 14, pp. 248-257 (1970); U.S. Patent No.
4,434,226, 4,414,310, 4,433,048, 4,43
It can be easily prepared by the methods described in US Pat. No. 9,520 and British Patent No. 2,112,157. The crystal structure of the silver halide grain in the present invention may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different halogen composition due to epitaxial junction. Silver halide may be bonded, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used. The emulsion in the present invention is a surface latent image type in which a latent image is mainly formed on the surface,
Either an internal latent image type formed inside the grains or a type having a latent image on both the surface and the inside may be used, but a negative emulsion is required. Of the internal latent image type,
And a core / shell type internal latent image type emulsion described in JP-A-264740. The method of preparing the core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like.
Is preferably from 40 to 40 nm, particularly preferably from 5 to 20 nm.

The silver halide emulsion used in the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure Nos. 17643, 18716 and
It is described in No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, the grain size of the photosensitive silver halide emulsion, grain size distribution, halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer. U.S. Pat.No. 4,082,553, silver halide grains having a fogged surface described in U.S. Pat.No. 4,626,498, silver halide grains having a fogged interior described in JP-A-59-214852, and colloidal silver are exposed. It can be preferably used for a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged inside or surface thereof" means silver halide grains which can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . A method for preparing silver halide grains having the inside or the surface of the grains is described in U.S. Pat.
No. 8, JP-A-59-214852. The silver halides forming the internal nuclei of the core / shell type silver halide grains whose insides are fogged 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 size of the fogged silver halide grains is not particularly limited, but the average grain size is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but may be monodispersed (at least 95% of the weight or number of silver halide grains is ± 40% of the average grain size). %).

In addition, it is preferable to use non-light-sensitive fine grain silver halide in the light-sensitive material of the present invention. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average particle size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The 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 grains does not need to be chemically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance.
Colloidal silver can be preferably contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 8.0 g / m ² or less, 6.0 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, page 866-868 Strong Color sensitizer 〜Page 649, right column 4. Brightening agent Page 24, 647, right column, page 868 5. Antifoggant, page 24-25, page 649, right column, 868-870, stabilizer 6.Light absorber, 25- Page 26 649 page right column 873 filter dye, ~ 650 page left column UV absorber 7.Stain inhibitor page 25 right column 650 page left column 872 ~ right column 8. Dye image stabilizer page 25 650 page left column 872 Page 9. Hardener page 26 page 651 left column page 874-875 10. Binder page 26 page 651 left column 873-874 11. plasticizer, page 27 page 650 right column page 876 lubricant 12. 26-27 page 650 right column 875-876 Surfactant 13. Antistatic agent 27 page 650 right column 876-877 14. Matsuto 878-879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, a compound capable of being fixed by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 is applied to the light-sensitive material of the present invention. It is preferably added to the material. In the light-sensitive material of the present invention, U.S. Patent Nos. 4,740,454 and 4,788,132, JP-A-62-18539
And a mercapto compound described in JP-A 1-283551. The photosensitive material of the present invention includes
It is preferable to include a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, irrespective of the amount of developed silver produced by the development processing described in Japanese Patent No. 106052. In the light-sensitive material of the present invention, International Publication WO88 / 0
No. 4794, a dye dispersed by the method described in JP-A-1-502912 or EP 317,308A, U.S. Pat.
No. 555 and JP-A-1-259358 are preferably contained.

The following various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure Nos. 17643, VII-CG and VII-CG and Nos. 307105 and VII. -Described in the patents described in CG. As the yellow coupler, for example, U.S. Patent Nos. 3,933,501, 4,022,620, 4,326,024, 4,4
01,752, 4,248,961, JP-B-58-10739, UK Patent 1,425,020, JP 1,476,760, US Patent 3,973,96
No. 8, No. 4,314,023, No. 4,511,649, European Patent No. 24
Those described in 9,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897, European Patent 73,636,
U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3
No. 3552, Research Disclosure No. 24230 (1984
June), JP-A-60-43659, JP-A-61-72238, JP-A-60-357
No. 30, No. 55-118034, No. 60-185951, U.S. Pat.
Nos. 0,630, 4,540,654, 4,556,630, International Publication WO8
What is described in 8/04795 etc. is especially preferable. Examples of cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212 and 4,146,396,
4,228,233, 4,296,200, 2,369,929, 2,8
01,171, 2,772,162, 2,895,826, 3,772,00
No. 2, 3,758,308, 4,334,011, 4,327,173,
West German Patent Publication No. 3,329,729, European Patent No. 121,365A,
No. 249,453A, U.S. Pat.Nos. 3,446,622, 4,333,999
Nos. 4,775,616, 4,451,559, 4,427,767,
Nos. 4,690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferred. Further, JP-A 64-553, JP-A 64-554, JP-A 64-555, pyrazoloazole couplers described in JP-A 64-556, and U.S. Pat.
No. 672 can also be used. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,
No. 282, No. 4,409,320, No. 4,576,910, UK Patent 2,10
2,137, EP 341,188A and the like.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,125,5
No. 70, European Patent No. 96,570, West German Patent (Published) No. 3,234,
Those described in No. 533 are preferred. A colored coupler for correcting unnecessary absorption of a coloring dye which can be used together with the above-mentioned yellow colored cyan coupler used in the present invention is described in Research Disclosure No. 17643 VI.
Sections I-G, VII-G of No. 307105, U.S. Pat.
No. 670, JP-B-57-39413, U.S. Pat.No. 4,004,929,
No. 4,138,258 and British Patent No. 1,146,368 are preferred. Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181 and a dye that can form a dye by reacting with a developing agent described in U.S. Pat.No.4,777,120 It is also preferable to use a coupler having a precursor group as a leaving group. Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing a development inhibitor, which can be used together with the above-mentioned DIR compound used in the present invention, is the above-mentioned R
D Nos. 17643, Sections VII-F and 307105, Patents described in Sections VII-F, JP-A-57-151944, JP-A-57-154234,
Nos. 60-184248, 63-37346, 63-37350 and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, UK Patent No. 2,097,140,
Preferred are those described in 2,131,188, JP-A-59-157638 and JP-A-59-170840. Also, JP-A-60-107029, 60-70
Compounds which release a fogging agent, a development accelerator, a silver halide solvent, etc. by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-252340, JP-A-1-44940 and JP-A-1-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competing couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,338,3
No. 93, 4,310,618 and the like, multi-equivalent couplers described in JP-A-60-185950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds or D
IR redox releasing redox compounds, EP 173,
Nos. 302A and 313,308A, couplers which release dyes which recolor after release, RD Nos. 11449 and 24241, JP-A-6241
Bleach accelerator releasing couplers described in 1-201247, ligand releasing couplers described in U.S. Pat.No. 4,555,477 and the like, couplers releasing leuco dyes described in JP-A-63-75747,
Couplers that release a fluorescent dye described in U.S. Pat. No. 4,774,181 are exemplified.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, for example, an oil-in-water dispersion method or a latex dispersion method. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid ester (Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-
Ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllauramide, N -Tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol) Tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octyl aniline, etc.),
And hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). Further, as the auxiliary solvent, the boiling point is about 30 ℃ or more, preferably 50 ℃ or more
Organic solvents having a temperature of 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide. Specific examples of the latex dispersion method, the effect and the latex for impregnation are described in U.S. Pat.No. 4,199,363 and West German patent application (OL
S) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol and 1,2-benzisothiazolin-3-one described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941 may be used. Add various preservatives or fungicides such as n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole Is preferred. 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 include, for example, the aforementioned R
D. No. 17643, page 28, No. 18716, page 647 right column to page 648 left column, and No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less,
23 μm or less is more preferable, 18 μm or less is further preferable, and 16 μm or less is particularly preferable. The film swelling speed T _1/2
Is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under humidity control at 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. Green et al., Photographic Science and Engineering (Photogr. Sci.
& Eng.), Vol. 19, No. 2, pp. 124-129.
_{For 1/2} , 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds is defined as the saturated film thickness, and 1/2 of the saturated film thickness.
Is defined as the time to reach. Film swelling speed T
_{The 1/2} can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above according to the formula: (maximum swelling film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The 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 ~ 5
00% is preferred.

The color photographic light-sensitive materials according to the present invention are described in RD No. 17643, pp. 28-29, RD No. 18716, pp. 651 left-right column, and RD No. 307105, pp. 880-881. The development can be carried out by the usual method. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N- ethyl-
β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, in particular, 3-methyl-4-amino-N-ethyl
-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in combination of two or more depending on the purpose. The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains an inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanedia Down tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
Nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples. .

When the reversal process is performed, color development is usually performed after black and white development. Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone in the black-and-white developer. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds. Typical bleaching agents are organic complex salts of iron (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid. Etc. can be used. Of these, iron (III) complex salts of ethylenediaminetetraacetate and iron (1,3-diaminopropanetetraacetate (II)
Iron (III) aminopolycarboxylate complex salts such as (I) complex salts are preferred from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH for speeding up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following publications: U.S. Pat. No. 3,893,858, West German Patent 1,290,812,
2,059,988, JP-A-53-32736, JP-A-53-57831, and 5
3-37418, 53-72623, 53-95630, 53-95631
No. 53-104232, No. 53-124424, No. 53-141623,
No. 53-28426, Research Disclosure No. 17129
Having a mercapto group or a disulfide group described in JP-A-50 / 140129 (July 1978); thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506; JP-A-52-20
No. 832, No. 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715, JP-A-58-16
Iodide salts described in No. 235; West German Patent Nos. 966,410 and 2,741
Polyoxyethylene compounds described in No. 8,430;
Polyamine compounds described in 5-8836; Others JP-A-49-409
No. 43, No. 49-59644, No. 53-94927, No. 54-35727, No.
Compounds described in Nos. 55-26506 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 in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858 and West German Patent No. 1,290,8
No. 12, JP-A-53-95630 are preferred. Further, the compounds described in U.S. 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 photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid, propionic acid, hydroxyacetic acid and the like. Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodides, and thiosulfates are generally used. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative for the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct or a sulfinic acid compound described in EP 294,769A is preferable. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution has a pKa of 6.0 to 9.
It is preferable to add 0.1 to 10 mol / l of a compound of the present invention, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole.

It is preferable that the total time of the desilvering step is shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible.
As a specific method of enhancing stirring, a method of impinging a jet of a processing solution on an emulsion surface of a photosensitive material described in JP-A-62-183460, or a method of stirring using a rotating means described in JP-A-62-183461 can be used. A method of increasing the effect, a method of moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and increasing the stirring effect by turbulently flowing the emulsion surface, and circulating the entire processing solution. There is a method of increasing the flow rate. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Among them, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and
Television Engineers, Vol. 64, pp. 248-253 (1955
Month) can be obtained. According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved by
The method for reducing calcium ions and magnesium ions described in 62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology"
(1982) The Fungicide described in "Encyclopedia of Bactericidal and Fungicides" (ed. 1986) edited by the Japan Society of Industrial Technology, Japan Society of Bacteria and Fungi. The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to 4.
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Patent Application Laid-Open
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used. Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
It is preferable to correct the concentration by adding water. The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Normally
A temperature of 33 ° C to 38 ° C is standard, but higher temperatures can accelerate the processing and shorten the processing time, and lower temperatures can improve the image quality and improve the stability of the processing solution. it can.

[0345]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 On an undercoated cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.60 ExM-1 0.11 ExF-1 3.4 × 10 ^-3 HBS-1 0.16

Second layer (intermediate layer) ExC-2 0.055 UV-1 0.011 UV-2 0.030 UV-3 0.053 HBS-1 0.05 HBS-2 0.020 Polyethyl acrylate latex 8.1 × 10 ^-2 gelatin 0.75

Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.46 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.0 × 10 ^-4 ExC-1 0.11 ExC-3 0.045 ExC-4 0.07 ExC-5 0.0050 ExC-7 0.001 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.090 Gelatin 0.87

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.0 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.13 ExC-2 0.055 ExC-4 0.085 ExC-5 0.007 ExC-8 0.009 Cpd-2 0.036 HBS-1 0.11 Gelatin 0.70

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E silver 1.62 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.125 ExC-3 0.040 ExC-6 0.010 ExC-8 0.014 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.60

Sixth layer (intermediate layer) Cpd-1 0.07 HBS-1 0.04 Polyethyl acrylate latex 0.19 Gelatin 1.30

Seventh layer (low-sensitivity green-sensitive emulsion layer) Emulsion A silver 0.24 Emulsion B silver 0.10 Emulsion C silver 0.14 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 0.005 ExM-2 0.30 ExM-3 0.09 ExY-1 0.015 HBS-1 0.26 HBS-3 0.006 Gelatin 0.80

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Emulsion D Silver 0.94 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.16 ExM-3 0.045 ExY-1 0.008 ExY-5 0.030 HBS-1 0.14 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high sensitivity green-sensitive emulsion layer) Emulsion E silver 1.29 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.011 ExM-1 0.016 ExM-4 0.046 ExM-5 0.023 Cpd-3 0.050 HBS-1 0.20 HBS-2 0.08 Polyethyl acrylate latex 0.26 Gelatin 1.57

Tenth layer (yellow filter layer) Yellow colloidal silver silver 0.010 Cpd-1 0.10 HBS-1 0.055 gelatin 0.70

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion C silver 0.25 Emulsion D silver 0.10 ExS-7 8.0 × 10 ^-4 ExY-1 0.010 ExY-2 0.70 ExY-3 0.055 ExY-4 0.006 ExY-6 0.075 ExC-7 0.040 HBS-1 0.25 Gelatin 1.60

12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F silver 1.30 ExS-7 3.0 × 10 ^-4 ExY-2 0.15 ExY-3 0.06 HBS-1 0.070 Gelatin 1.13

Thirteenth layer (first protective layer) UV-2.08 UV-3 0.11 UV-4 0.26 HBS-1 0.09 Gelatin 2.40

Fourteenth layer (second protective layer) Emulsion G silver 0.10 H-1 0.37 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-3 0.10 S-1 0.20 Gelatin 0.75

In order to improve the storability, processability, pressure resistance, fungicide / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-3, B-4 to B- 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains iridium, palladium and rhodium salts.

[0362]

[Table 1]

In Table A, (1) Emulsions A to F were prepared according to the examples of JP-A-2-19938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to F were prepared according to the examples in JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

[0364]

Embedded image

[0365]

Embedded image

[0366]

Embedded image

[0367]

Embedded image

[0368]

Embedded image

[0369]

Embedded image

[0370]

Embedded image

[0371]

Embedded image

[0372]

Embedded image

[0373]

Embedded image

[0374]

Embedded image

[0375]

Embedded image

[0376]

Embedded image

[0377]

Embedded image

[0378]

Embedded image

[0379]

Embedded image

[0380]

Embedded image

Preparation of Sample 102 A sample was prepared by making the following changes to Sample 101. The iodine content of the third layer emulsion A was changed from 2 mol% to 3.5 mol%. The iodine content of the fourth layer emulsion D is from 4.1 mol% to 7.
Changed to 15 mol%. The iodine content of the fifth layer emulsion E is from 3.4 mol% to 5.
Changed to 93 mol%. The iodine content of the seventh layer emulsion A is from 2 mol% to 3.5 mol%, and the iodine content of the emulsion C is 3.0 mol% to 5.0 mol%.
Changed to 3 mol%. The iodine content of the eighth layer emulsion D is from 4.1 mol% to 7.
Changed to 15 mol%. The ninth layer emulsion E has an iodine content of 3.4 mol% to 5.
Changed to 93 mol%. -The silver coating amounts of the third, fourth, fifth, seventh, eighth and ninth layers were respectively 1.2 times.

Preparation of Sample 103 A sample was prepared by making the following changes to Sample 101. The iodine content of the third layer emulsion A was changed from 2 mol% to 4.7 mol%. The iodine content of the fourth layer emulsion D is from 4.1 mol% to 9.
Changed to 6 mol%. The iodine content of the fifth layer emulsion E is from 3.4 mol% to 8.
Changed to 01 mol%. The iodine content of the seventh layer emulsion A is from 2 mol% to 4.7 mol%, and the iodine content of the emulsion C is 3.0 mol% to 7.0 mol%.
It changed to 06 mol%. The iodine content of the eighth layer emulsion D is from 4.1 mol% to 9.
Changed to 60 mol%. The ninth layer emulsion E has an iodine content of 3.4 mol% to 8.
Changed to 01 mol%. The silver coating amounts of the emulsions of the third, fourth, fifth, seventh, eighth and ninth layers were each 1.35 times.

Preparation of Sample 104 A sample was prepared by making the following changes to Sample 101. The iodine content of the third layer emulsion A is from 2 mol% to 0.87
Changed to mol%. The iodine content of the fourth layer emulsion D is from 4.1 mol% to 1.
It was changed to 79 mol%. The iodine content of the fifth layer emulsion E is from 3.4 mol% to 1.
It was changed to 49 mol%. The iodine content of the seventh layer emulsion A is from 2 mol% to 0.87
The iodine content of the emulsion C was changed from 3.0 mol% to 1.31 mol%. -The iodine content of the eighth layer emulsion D is from 4.1 mol% to 1.
It was changed to 79 mol%. The ninth layer emulsion E has an iodine content of 3.4 mol% to 1.
It was changed to 49 mol%. -The silver coating amounts of the emulsions of the third, fourth, fifth, seventh, eighth and ninth layers were each 0.85 times.

Preparation of Sample 105 A sample was prepared by making the following changes to Sample 101. The emulsion and material coating amounts of the fifth, ninth and twelfth layers are each set to 0.1
45 times.

Preparation of Sample 106 A sample was prepared by making the following changes to Sample 101. The third and fourth layers of ExC-5 (yellow colored cyan coupler) were changed to equimolar ExC-3. -ExC-8 of the third, fourth and fifth layers was changed to ExC-9 of equimolar. -The material application amounts of all the eleventh layers were each set to 0.85 times.

Preparation of Sample 107 A sample was prepared by making the following changes to Sample 101. The third and fourth layers of ExC-5 (yellow colored cyan coupler) were changed to equimolar ExC-3. -The application amounts of all the materials of the eleventh layer were respectively 0.92 times.

Preparation of Sample 108 A sample was prepared by making the following changes to Sample 101. -ExC-8 of the third, fourth and fifth layers was changed to ExC-9 of equimolar. -The application amounts of all the materials of the eleventh layer were respectively 0.92 times.

Preparation of Sample 109 A sample was prepared by making the following changes to Sample 101. The amount of the emulsion in the fifth, ninth and twelfth layers was increased 2.5 times, and the amount of the applied material in the fifth, ninth and twelfth layers was doubled.

Preparation of Film with Lens The samples 101 to 109 prepared as described above were processed into a 135 format, reloaded into Fujifilm's “Sharunada Econoshot FLASH”, and made ready for photography.

Imaging The following imaging was performed using the film with a lens prepared as described above. 1) A color rendition chart of Macbeth Co., Ltd. was photographed under clear daylight (LV value: about 13) to prepare materials for evaluating color saturation and granularity. 2) In order to evaluate the descriptive power and the color saturation of a dark part, a woman was photographed with a Macbeth color rendition chart under slightly cloudy conditions (LV value: about 10). 3) In order to evaluate the descriptive power of the dark area and the color saturation, the shooting distance was changed to 1 m, 3 m, 4 m, and 5 m using a strobe in the night room, and the woman was photographed with a Macbeth color rendition chart. .

Developing and Printing The photographed film was developed with an automatic developing machine FP-560B for mini lab manufactured by FUJIFILM Corporation. Next, a printer processor PP-12 for minilab manufactured by Fujifilm Corporation
L size prints were made with 5OV (nicknamed Rocky).

Evaluation of Print The L-size print prepared as described above was evaluated for dark area descriptive power, color saturation, graininess, and overall satisfaction including the above three points. The results are shown in Table-B. In addition, Table-B also shows the evaluation results of the interlayer suppression effect and the specific photographic sensitivity.

[0393]

[Table 2]

[0394]

[Table 3]

As is clear from Table-B, Sample 10 satisfying the conditions for the interlayer suppression effect of the present invention and the specific photographic sensitivity
With respect to 1, 107 and 108, very satisfactory results were obtained, and the effect of the present invention was confirmed.

Example 2 The yellow colored cyan coupler ExC-5 of the third and fourth layers of the sample 101 was replaced with an equimolar yellow colored cyan coupler YC-24 by the third, fourth and fifth layers. A sample was prepared by changing ExC-7 belonging to the general formula (2) to CB-25, and this was designated as Sample 201. This sample 20
Comparative Samples 202 to 209 similar to those in Example 1 were prepared for Sample No. 1, and the same evaluations as in Example 2 were performed on Samples 201 to 209. As a result, as in the case of Example 1, a sample satisfying the conditions for the interlayer suppression effect of the present invention and the specific photographic sensitivity obtained a very satisfactory result, and the effect of the present invention was confirmed again.

[0397]

According to the silver halide color photographic light-sensitive material satisfying the conditions for the interlayer suppression effect and the specific photographic sensitivity according to the present invention, a color image excellent in comprehensive evaluation including darkness descriptive power, color saturation, and graininess can be obtained. Was done.

[Brief description of the drawings]

FIG. 1 is a characteristic curve for obtaining a magnitude IE (X / Y) of an interlayer suppression effect.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI G03C 7/305 G03C 7/305 7/333 7/333 (72) Inventor Masayoshi Toyoda 210 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fujifilm Shin Film (56) References JP-A-1-182847 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 7/20

Claims (5)

(57) [Claims] 1. A color photographic light-sensitive material having at least one red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layer on a support, each having a layer suppressing effect IE (X
/ Y) is 0.15 <IE (R / G), −0.05 <IE (R / G)
B) 0.10 <IE (G / R), 0.15 <IE (G / R)
B) 0.03 <IE (B / G), 0.03 <IE (B / G)
R) and a characteristic photographic sensitivity of 640 to 2,000. 2. The silver halide color photographic light-sensitive material according to claim 1, comprising a compound represented by the following general formula (1) and / or general formula (2). Formula _{(1) A- (L 1)} j - (L 2) m - in _{[(L 3) n -PUG]} s formula, A represents a coupler residue or a redox group, L ₁
And L ₃ represents a divalent timing group; L ₂ represents a timing group having a trivalent or higher bond;
UG represents a photographically useful group. j and n each independently represent 0, 1 or 2; m represents 1 or 2;
It is a number obtained by subtracting 1 from the valence of ₂ , and represents an integer of 2 or more.
When a plurality of L ₁ , L ₂ or L ₃ are present in a molecule, they may be all the same or different. The plurality of PUGs may all be the same or different. In the general formula _{(2) A-L 4 -L} 5 -PUG formula, A and PUG are as in formula (1) synonymous. L ₄ represents a —OCO— group, a —OSO— group, a —OSO ₂ — group, a —OC
S-group, -SCO- group, -SCS- group or -WCR ₁₁
R ₁₂ represents a group. Here, W represents an oxygen atom, a sulfur atom or a tertiary amino group (—NR ₁₃ —), and R ₁₁ and R ₁₂
Each independently represents a hydrogen atom or a substituent, and R ₁₃ represents a substituent. And any two of R ₁₁ , R ₁₂ and R ₁₃
One represents a divalent group, and includes the case where they are linked to form a cyclic structure. And L ₅ represents a group defined by a group or L ₄ releases PUG by electron transfer along a conjugated system. 3. The silver halide color photographic material according to claim 1, which contains a yellow colored cyan coupler. 4. The silver halide grains of the all red-sensitive layer and / or the all green sensitive layer have an average iodine content of 2 to 5 mol%.
The silver halide color photographic light-sensitive material according to any one of claims 1 to 3, further comprising a silver halide grain. 5. A selenium-sensitized tabular silver halide emulsion having at least 50% of the total projected area having dislocation lines having an aspect ratio of 3 or more and being selenium-sensitized in a red-sensitive layer and a green-sensitive layer. The silver halide color photographic light-sensitive material according to any one of claims 1 to 4, wherein the material is contained.