JPH06222524A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance graininess, sharpness, and color reproduction performance, to obtain sufficient rise of sensitivity at the time of sensitization processing and to make a balance of gradation close to that at the time of standard development by forming a specified emulsion layer. CONSTITUTION:The unit of the silver halide emulsion layers contains a flat monodispersion emulsion having a prescribed structure and the average silver iodide content of the emulsion layer having the maximum sensitivity is not more than that of the other emulsion layers in the same unit, and that of the unit of the photosensitive emulsion layers nearest to the light incident side is 0-3mol% and not more than those of the other emulsion layer units, and this photosensitive material contains at least one of compounds represented by the formula in which A is an oxidation-reduction nucleus or its precursor permitting (Time)tX not to be released until it is oxidized in development processing; Time is a group releasing X after it is released from the oxidation product of A; X is a development inhibitor; L is a divalent bonding group; G is a polarizable group; and each of(n), (m) and (t) is 0 or 1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material excellent in sharpness, graininess and sensitized development characteristics.

[0002]

2. Description of the Related Art In silver halide color photographic light-sensitive materials, the development of techniques for improving image quality is an important issue. In recent years, means for achieving high image quality in a small format have been developed one after another, but it is not sufficient yet, and further technical improvement is required.

Usually, in a multilayer color photographic material having blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers, it is known that light scattering by silver halide grains tends to reduce the sharpness of the emulsion layer located below. Has been. U.S. Pat. No. 4,4
Nos. 34,226 and 4,439,520 describe color photographic light-sensitive materials having improved sharpness, sensitivity and graininess by using tabular silver halide emulsion grains. U.S. Pat. No. 4,433,048 discloses that tabular grains having an AgI distribution in the grains increasing from the center toward the surface exhibit excellent sensitivity and size ratio.

Further, in JP-A-62-18552, silver halide grains contained in all silver halide emulsion layers are composed of silver iodobromide containing 4 mol% or less of silver iodide. It is disclosed that a color photographic light-sensitive material containing tabular silver halide grains in at least one layer has excellent color reproducibility. On the other hand, JP-A-62-1855
No. 6 shows that the photosensitive material using monodisperse tabular silver halide grains has excellent image sharpness and graininess as compared with those using polydisperse tabular grains, and JP-A-63-15161.
No. 8 discloses a method for preparing the monodisperse tabular grains. Further, JP-A-2-256043 discloses that image sharpness and graininess are improved by using a monodisperse tabular emulsion having an improved AgI distribution between silver halide emulsion grains, and EP-0514743A1. In the issue,
A method of improving the sharpness by an emulsion that defines the tabularity has been proposed. However, even when these monodisperse tabular emulsions were used, the sharpness on the low frequency side was not sufficiently improved. Also, the use of so-called tabular grains tends to reduce the interlayer effect and impair the reproduction of highly saturated colors. Further, when the sensitized development for obtaining high sensitivity is performed by extending the development time, the gradation becomes harder than that in the standard development, so that the gradation reproduction is deteriorated and the improvement is demanded. Further, it has been demanded that the sensitivity increase width upon sensitized development is sufficient.

On the other hand, as another means other than the above, the sharpness,
In particular, the use of DIR compounds for improving the edge effect is generally performed at present, but the commonly used ones release a development inhibitor imagewise by a coupling reaction with an oxidation product of a color developing agent. It is a DIR coupler that forms a colored dye.

However, when a DIR coupler is used, if the dye formed by the coupling reaction is different from the dye obtained from the main coupler, color turbidity occurs, which is not preferable for color reproduction. To prevent this, a DIR having a hue similar to that of the main couplers of yellow, magenta, and cyan.
It is necessary to develop a coupler, but it is also necessary to develop three types of compounds having optimal reactivity, and the development and synthesis cost burden increases, so a colorless DIR compound has been demanded. .

Colorless DIR compounds are classified into two types, a coupling type and a redox type, depending on the reaction mode with an oxidant of a color developing agent. Of these, the coupling type is disclosed in Japanese Examined Patent Publications No. 51-16141 and No. 51-1.
6142, U.S. Pat. Nos. 4,226,943, 41712.
Nos. 3,379,529 and 3,639,417, and Japanese Patent Laid-Open No. Sho 49-49, regarding the compounds described in JP-A No. 23, etc. and the redox type compounds.
No. 129536, No. 64-546, and Japanese Patent Application No. 2-21
127, etc., or JP-A-61-213847 and 64-88451.
And U.S. Pat. No. 4,684,604 and the like, there are DIR hydrazide compounds. When the processing step is applied to a color reversal light-sensitive material composed of B / W development (first development) and color development (second development), it is preferable to release the inhibitor from the DIR compound in the first development. This is because the second development is aimed at rapidly developing all the silver halide that has not been developed in the first development, and therefore the silver development speed is extremely high. For this reason, if it is attempted to exert an imagewise effect of suppressing development in the second development, silver development is delayed and processing instability in color development is introduced, which is not preferable. Therefore, it is preferable to react a DIR compound in the first development, but in this case, it is essential to use a redox DIR compound that can also react with an oxidized product of a B / W developing agent.

However, when the above-mentioned DIR compound is used, it is difficult to obtain sufficient sensitization suitability because the sensitivity increase width during sensitized development is narrowed and the gradation balance tends to be disturbed.

[0009]

Therefore, the object of the present invention is to provide excellent graininess, sharpness, color reproducibility, sufficient sensitivity increase during sensitization processing, and tone balance as compared with standard development. To obtain a near color photographic light-sensitive material.

[0010]

The objects of the present invention have been achieved by the following means. 1) In a photographic light-sensitive material having a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer unit comprising one or more emulsion layers on a support, at least one of the emulsion layers has an average aspect ratio of 2 or more. The average silver iodide content of the emulsion layer containing the tabular monodisperse emulsion having a structure depending on the difference in halogen composition and having the highest sensitivity among the emulsion layers constituting the emulsion layer unit in at least one emulsion layer unit is The average silver iodide content of the other emulsion layers in the same unit is less than the average silver iodide content of the photosensitive emulsion layer unit closest to the incident light side is 0 to 3 mol%, and the other emulsion layer units A silver halide color photographic light-sensitive material having a mean silver iodide content of not more than 1 and containing at least one compound represented by the following general formula (F).

General formula (F)

[0012]

[Chemical 4] In the formula, A represents a redox mother nucleus or a precursor thereof, and is not oxidized until it is oxidized (Tim.
e) Represents an atomic group that allows _t X to leave. Time represents a group that releases X after being released from the oxidant of A, and X represents a development inhibitor. L represents a divalent linking group, and G represents a polarizable group. n, m, and t each represent 0 or 1.

2) The color photographic light-sensitive material as described in 1) above, which comprises the compound of formula (F) in a substantially non-photosensitive intermediate layer adjacent to the light-sensitive emulsion layer.

3) A block polymer of a hydrophobic polyalkylene oxide represented by the following general formula (I) and a hydrophilic polyalkylene oxide represented by the general formula (II) in at least one photosensitive emulsion layer. A general formula (I) characterized by containing a polymer having

[0015]

[Chemical 5] General formula (II)

[0016]

[Chemical 6] The color photographic light-sensitive material as described in 1) or 2) above.

4) The color photographic light-sensitive material as described in 1) to 3) above, which is imagewise exposed to a B / W development step and then color-developed to obtain a positive image.

The present invention will be described in detail below.

The tabular grain in the present invention means that it has two substantially parallel surfaces, and the thickness of the grain is expressed by the distance between the two parallel planes. The diameter of the particle is represented by the diameter of a circle having an area equal to the projected area of the particle. The aspect ratio of the particles means the ratio of the diameter and the thickness of the particles. A tabular emulsion is an emulsion mainly composed of such tabular grains and has an average aspect ratio of 1
It means the average value of the aspect ratio of tabular grains accounting for 50% or more of the projected area of all emulsion grains contained in one emulsion.
The tabular emulsion used in the present invention has an average aspect ratio of 2 or more, preferably 5 or more, and may be 8 or more.

The monodisperse emulsion is one having a variation coefficient vc of 25% or less, which is obtained by dividing the standard deviation S of the diameter of a circle equal to the projected area of all the grains contained in the emulsion by the average grain size r, but not more than 25%. Is 20% or less, more preferably 15% or less. The above-mentioned particle size can be measured, for example, by the method described in Chapter 2 of "Theory of Photographic Process" by Mies and James, 3rd edition, published by Kumamiran (1966).

The monodisperse tabular emulsion can be prepared, for example, by the method described in US Pat. No. 4,797,354. Further US Pat. No. 514777
No. 1, No. 5147772, and No. 514777.
No. 3 shows that a good monodisperse emulsion can be obtained by using a polyethylene oxide block copolymer. The polymers used in the present invention are described below.

In the photographic light-sensitive material of the present invention, a particularly useful compound for preparing a silver halide emulsion is a hydrophobic polyalkylene oxide represented by the following general formula (I) and the following general formula (II). Is a polymer having a hydrophilic polyalkylene oxide block polymer component represented by

General formula (I)

[0024]

[Chemical 7] General formula (II)

[0025]

[Chemical 8] In the formula, R ¹ represents a hydrogen atom, alkyl having 1 to 10 carbons (eg, methyl, chloromethyl, ethyl, n-butyl), aryl having 6 to 10 carbons (eg, phenyl, naphthyl), and n is 1 Represents an integer from 1 to 10. Where n =
When 1, R ¹ is never a hydrogen atom.

R ² represents a hydrogen atom or a lower alkyl group having 4 or less carbon atoms (eg hydroxymethyl, carboxymethyl) substituted with a hydrophilic group (eg hydroxy, carboxyl).

X and y represent the number of repetitions of each unit (number average degree of polymerization). For x and y, depending on the structure of the polymer,
Although the preferable range is different, x is 2 to 1000, preferably 3 to 500, and y is 1 to 100.
It is 0, preferably 2 to 400.

The proportions of the components of the general formula (I) and the general formula (II) in the block polymer may vary depending on the hydrophilicity / hydrophobicity of each unit and the type of emulsion prepared.
Roughly speaking, the weight ratio is within the range of 4:96 to 96: 4.

Among the hydrophobic polyalkylene oxides of the general formula (I), polypropylene oxide (R ¹ = methyl, n = 1) is particularly preferable, and the hydrophilic polyalkylene oxide of the general formula (II) is preferable. Is polyethylene oxide (R ² = hydrogen atom), polyglycerol (R ² = CH ₂ OH), and particularly preferred is polyethylene oxide.

With respect to the polymer having the above block copolymer component in the molecule, a compound having polypropylene oxide-polyethylene oxide as a typical component as a block copolymer component will be described in more detail below.

Representative examples of polymers used in the present invention are:
It can be represented by the following general formulas (III) to (X).

General formula (III)

[0033]

[Chemical 9] General formula (IV)

[0034]

[Chemical 10] General formula (V)

[0035]

[Chemical 11] General formula (VI)

[0036]

[Chemical 12] General formula (VII)

[0037]

[Chemical 13] General formula (VIII)

[0038]

[Chemical 14] General formula (IX)

[0039]

[Chemical 15] General formula (X)

[0040]

[Chemical 16] Among the general formulas (III) to (X), x, x ′, x ″,
x ''', y, y', y '', y '''represents the repeating number of each unit, and its preferable range is x of the general formulas (I) and (II),
Same as y. R ³ represents a monovalent group, specifically a hydrogen atom, a substituted or unsubstituted alkyl or aryl, and preferably a substituted or unsubstituted lower alkyl group (having 6 or less carbon atoms). Specific examples of R ³ include methyl, ethyl, n-propyl, isopropyl, t-butyl, chloromethyl, methoxycarbonylmethyl, N-methyl N-ethylaminoethyl and N, N-diethylaminoethyl.

L represents a trivalent or tetravalent linking group.
Specific examples of L are shown below, but the present invention is not limited to these.

[0042]

[Chemical 17]

[0043]

[Chemical 18] Hereinafter, Tables 1 and 2 show specific examples of the polymer having a block polymer component in the molecule used in the present invention, but the present invention is not limited thereto.

[0044]

[Table 1]

[0045]

[Table 2] For specific examples, general description of the above-mentioned polymers used in the present invention, and for specific examples of preparation of silver halide emulsions using this type of polymer, European Patent Publication Nos. 513722, 513723, 513724, 5
13725, 513742, 513743, 51806
6 etc. can be mentioned.

These polymers are used in the process of forming tabular silver halide grains in an amount of not more than 100% by weight, preferably 20% by weight, based on the amount of silver used for forming tabular nuclei.
Used below. Further, it is desirable to add the above amount before the start of grain formation, and it may be added additionally during the growth process of tabular grains.

The emulsion used in the present invention has a halogen composition of silver haloiodide, but silver iodobromide is preferred. The silver iodide content is 40 mol% or less, preferably 10 mol% with respect to silver.
Or less, more preferably 5 mol% or less. In order to realize the preferred multilayer effect of the present invention, the emulsion layer having the highest sensitivity among the emulsion layers constituting each emulsion layer unit has the average silver iodide content of the other emulsion layers in the same unit. Must be below the content. The average silver iodide content of the emulsion layer unit closest to the incident light side is 3 mol% or less, preferably 2.5 mol% or less. The average silver iodide content of the second and third emulsion layer units from the incident light side is determined by the required interlayer effect.

The content of the tabular monodisperse emulsion of the present invention is not particularly limited, but is 50 with respect to the Ag amount of the emulsion layer to be added.
% Or more is preferable because the effect of the present invention is remarkable. Further, it is preferable to mix and use the following emulsions in terms of design of gradation and the like.

The photosensitive emulsion other than the tabular monodisperse emulsion can be composed of a tabular polydisperse emulsion having an average aspect ratio of 2 or more, a non-tabular twin polydisperse or monodisperse emulsion, and a regular monodisperse emulsion. Regular monodisperse emulsions are cubic, octahedral, 1
It is usually composed of a dihedron, a tetrahedron, and a surface in which these crystal habits are mixed, and the corners may or may not be rounded. Further, the surface is not necessarily flat and may have irregularities or protrusions. Further, it may be bonded to a crystal part having a different halogen composition epitaxially on a face, a ridge or a vertex, or a compound other than silver halide such as silver rhodanide or lead oxide.

It is preferable that all emulsions used in the present invention have a structure having different compositions inside the grains. The difference in composition is preferably due to the difference in AgI content.
It is preferable that the maximum value of I is inside the particle. The maximum value may be one or two or more. The high AgI
The AgI content of the phase is the average Ag in the emulsion containing the grains.
It is more than twice the I content and 100% AgI. Furthermore, each emulsion preferably has one or more dislocation lines inside the grains, more preferably 10 or more dislocation lines. The dislocation lines may be uniformly present in the grains, may be localized in a part or a plurality of phases forming a structure, and may be concentrated in the outermost phase or a part thereof. The latent image forming site of the photosensitive emulsion may be mainly on the surface or inside, and may be on both the surface and inside, but it is necessary to be a negative emulsion. Of the internal latent image type,
The core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used. A method for preparing this 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, but is preferably 3 to 40 nm, and 5 to 20 n
m is particularly preferred.

Each photosensitive emulsion layer is formed by one or more emulsions. When a plurality of tabular emulsions are mixed, the average aspect ratio of the higher sensitive emulsion is preferably higher than that of the lower sensitive emulsion. The silver iodide content of the higher-sensitive emulsion is preferably lower than that of the lower-sensitive emulsion. A mixture of a tabular emulsion and a non-tabular twin crystal emulsion or a regular emulsion is also preferably used. It is particularly preferable to use a plurality of regular emulsions, especially when the average grain size is 0.4 μm or less, in terms of the design of the gradation of the highlight portion.

The light-sensitive material having the above-mentioned emulsion constitution can remarkably exert its effect in a color reversal photographic light-sensitive material.

Next, the compound represented by formula (F) in the present invention will be described in detail below.

The redox mother nucleus represented by A is ke
According to the ndall-Pelz rule, for example, hydroquinone, catechol, p-aminophenol, o-aminophenol, 1,2-naphthalenediol, 1,4-
Naphthalene diol, 1,6-naphthalene diol,
Mention may be made of 1,2-aminonaphthol, 1,4-aminonaphthol, 1,6-aminonaphthol, gallic acid ester, gallic acid amide, hydrazine, hydroxylamine, pyrazolidone or reductone.

The amino group contained in these redox mother nuclei is a sulfonyl group having 1 to 25 carbon atoms or 1 to 25 carbon atoms.
It is preferably substituted with the acyl group of. As the sulfonyl group, a substituted or unsubstituted aliphatic sulfonyl group,
Alternatively, an aromatic sulfonyl group can be mentioned. Examples of the acyl group include a substituted or unsubstituted aliphatic acyl group and aromatic acyl group. The hydroxyl group or amino group forming the redox mother nucleus of A may be protected by a protecting group that can be deprotected during development processing. Examples of the protecting group are those having 1 to 25 carbon atoms, such as an acyl group, an alkoxycarbonyl group, a carbamoyl group, and further JP-A-59-59.
-197037 and the protecting groups described in JP-A-59-201057. Furthermore, this protecting group is
If possible, the substituents of A described below may be bonded to each other to form a 5-, 6-, or 7-membered ring.

In the redox mother nucleus represented by A, a substitutable position may be substituted with a substituent. Examples of these substituents are those having 25 or less carbon atoms, such as alkyl, aryl, alkylthio, arylthio, alkoxy, aryloxy, amino, amide, sulfonamide, alkoxycarbonylamino, ureido, carbamoyl, alkoxycarbonyl, sulfamoyl, Sulfonyl, cyano, halogen atom, acyl, carboxyl,
Sulfo, nitro, heterocyclic residue or-(L) _n-
(G) _m- (Time) _tX . These substituents may be further substituted with the above-mentioned substituents. If possible, these substituents may be bonded to each other to form a saturated or unsaturated carbocycle or a saturated or unsaturated heterocycle.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, o-aminophenol, 1,4-naphthalenediol, 1,4-aminonaphthol, gallic acid ester, gallic acid amide, and hydrazine. To be A is more preferably hydroquinone, catechol, p-aminophenol, o-aminophenol or hydrazine, and most preferably hydroquinone or hydrazine.

L represents a divalent linking group, and preferably includes alkylene, alkenylene, arylene, oxyalkylene, oxyarylene, aminoalkyleneoxy, aminoalkenyleneoxy, aminoaryleneoxy and oxygen atom.

G represents an acidic group and is preferably the following (Chemical Formula 19).

[0060]

[Chemical 19] Wherein R ₁₅ is alkyl, aryl or heterocycle,
R ₁₆ has the same meaning as hydrogen atom or R ₁₆ . G is more preferably the following (Chemical formula 20), and most preferably the following (Chemical formula 21).

[0061]

[Chemical 20]

[0062]

[Chemical 21] n and m are 0 or 1, and which is preferable depends on the type of A. For example, when A is hydroquinone, catechol, aminophenol, naphthalenediol, aminonaphthol or gallic acid, n = 0 is preferable, and n = m = 0 is more preferable.

When A is hydrazine or hydroxylamine, n = 0 and m = 1 are preferable, and when A is pyrazolidone, n = m = 1 is preferable.

[0064] - (Time) _t -X is the first time that the redox mother nucleus in the formula (F) represented by A becomes an oxidized form undergoes development at cross oxidation - (Time) _t
It is a group released as -X.

It is preferable that Time is linked to G by a sulfur atom, a nitrogen atom, an oxygen atom or a selenium atom.

Thereafter, Time represents a group capable of further releasing X, may have a timing adjusting function, and may further be a coupler or redox group which releases X by reacting with an oxidized product of a developing agent. Good. When used in a color reversal sensitive material, a redox group is preferred.

When Time is a group having a timing adjusting function, for example, US Pat. No. 4,248,962,
U.S. Pat. No. 4,409,323, British Patent No. 2,096,7.
83, US Pat. No. 4,146,396, JP-A-51
Examples thereof include those described in JP-A-146828 and JP-A-57-56837. The Time may be a combination of two or more selected from those described in these.

Preferred examples of the timing control group include:
The following are listed. (1) Group Utilizing Cleavage Reaction of Hemiacetal For example, US Pat. No. 4,146,396, JP-A-60.
No. 249148 and No. 60-249149, it is a group represented by the following (Chemical Formula 22). here*
The mark represents the position bonded to the left side in the general formula (F), and the ** mark represents the position bonded to the right side in the general formula (F).

[0069]

[Chemical formula 22] In the formula, W is an oxygen atom, a sulfur atom or -N (R ₆₇ )-
Represents a group, R ₆₅ and R ₆₆ represent a hydrogen atom or a substituent, R ₆₇ represents a substituent, and t represents 1 or 2. When t is 2 the two _{-W-C (R 65) (} R 66) - represents the same or different. R ₆₅ and R ₆₆
Is a substituent and typical examples of R ₆₇ are
₆₉ groups, R ₆₉ CO- groups, R ₆₉ SO ₂ -groups, N (R ₆₉ ) (R
₇₀₎ CO- group, or _{N (R 69) (R 70} ) SO 2 - , etc. group. Here, R ₆₉ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Each of R ₆₅ , R ₆₆ and R ₆₇ represents a divalent group and is also included when they are linked to each other to form a cyclic structure. (2) Group for causing cleavage reaction utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,962 can be mentioned, which can be represented by the following Chemical Formula 23.

[0070]

[Chemical formula 23] In the formula, * mark represents a position bonded to the left side in the general formula (F), ** mark represents a position bonded to the right side in the general formula (F), Nu represents a nucleophilic group, an oxygen atom or a sulfur atom. An atom is an example of a nucleophilic group, E represents an electrophilic group, and is a group capable of cleaving the bond with the ** mark by a nucleophilic attack from Nu. Link is an intramolecular nucleophilic substitution of Nu and E. Represents a linking group that is sterically related so that it can react. (3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system, for example, US Pat. Nos. 4,409,323 or 4,4.
No. 21,845 and is a group represented by the following (Chemical formula 24).

[0071]

[Chemical formula 24] In the formula, *, **, W, R ₆₅ , R ₆₆ and t are
It has the same meaning as described in 1). (4) Group Utilizing Cleavage Reaction by Ester Hydrolysis For example, a connecting group described in West German Patent Publication No. 2,626,315, which is represented by the following (Chemical Formula 25). In the formula, the * mark and the ** mark have the same meanings as described for (Chemical Formula 22).

[0072]

[Chemical 25] (5) Group Utilizing Iminoketal Cleavage Reaction For example, a linking group described in US Pat. No. 4,546,073, which is a group represented by the following (Chemical Formula 26).

[0073]

[Chemical formula 26] In the formula, * mark, ** mark and W have the same meanings as described in (Formula 22), and R ₆₆ has the same meaning as R ₆₇ .

Examples of the group represented by D being a coupler or a redox group include the following.

As the coupler, for example, in the case of a phenol type coupler, the one bonded to G in the general formula (F) at the oxygen atom excluding the hydrogen atom of the hydroxyl group.
In the case of a 5-pyrazolone type coupler, G is bonded at an oxygen atom obtained by removing a hydrogen atom from a hydroxy group of a tautomerism of 5-hydroxypyrazole. Each of these functions as a coupler only after leaving from G, reacts with the oxidized form of the developing agent, and releases X bonded to their coupling positions.

Preferred examples of the case where Time is a coupler include the following (formula 27).

[0077]

[Chemical 27] In the formula, V ₁ and V ₂ represent a substituent, and V ₃ , V ₄ ,
V ₅ and V ₆ represent a nitrogen atom or a substituted or unsubstituted methine group, V ₇ represents a substituent, x represents an integer of 0 to 4, and when x is plural, V ₇ is the same or different. And two V _7's may be linked to each other to form a cyclic structure. V ₈ is a —CO— group, —SO ₂ —
Represents a group, an oxygen atom or a substituted imino group, V ₉ represents a non-metal atom group for forming a 5-membered to 8-membered ring,
V ₁₀ represents a hydrogen atom or a substituent.

When the group represented by Time in the general formula (F) is a redox group, it is preferable that
It is represented by 8).

[0079]

[Chemical 28] In the formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, at least one of k Y and Z represents a methine group having X as a substituent, and other Y and Z Represents a substituted or unsubstituted methine group or a nitrogen atom, k represents an integer of 1 to 3 (k Y and Z represent the same or different), and B can be removed by a hydrogen atom or an alkali. Represents a group. Here, the case where any two substituents of P, Y, Z, Q and B are combined into a divalent group to form a cyclic structure is also included. For example, (Y = Z) _k forms a benzene ring, a pyridine ring, or the like.

When P and Q represent a substituted or unsubstituted imino group, it is preferably an imino group substituted with a sulfonyl group or an acyl group.

At this time, P and Q are represented by the following (Chemical formula 29).

[0082]

[Chemical 29] Here, the * mark represents the position to be bonded to G of the general formula (F) or the position to be bonded to B of (Chemical Formula 28), and the ** mark is (Y
= Z) represents the position of bonding with one of the free bonds of _k- .

In the formula, the group represented by G ¹ represents an aliphatic group, an aromatic group or a heterocyclic group. Among the groups represented by (Chemical Formula 28), particularly preferable groups are those represented by the following (Chemical Formula 30) or (Chemical Formula 31).

[0084]

[Chemical 30]

[0085]

[Chemical 31] In the formula, the * mark represents the position of bonding with G in the general formula (F), and the ** mark represents the position of bonding with X.

R ₆₄ represents a substituent, and q represents an integer of 0, 1 or 3. When q is 2 or more, two or more R _64's may be the same or different, and when two R _64's are substituents on adjacent carbons, they are each a divalent group and are linked to each other to represent a cyclic structure. It also includes cases.

X means a development inhibitor. As a preferable example of X, a compound having a mercapto group bonded to a heterocycle represented by the following (Chemical Formula 32) or the following (Chemical Formula 3)
The heterocyclic compound represented by 3) capable of producing iminosilver is exemplified.

[0088]

[Chemical 32]

[0089]

[Chemical 33] In the formula, Z ₁ represents a group of non-metal atoms necessary for forming a monocyclic ring or a condensed ring heterocycle, and Z ₂ together with N forms a group of nonmetallic atoms necessary for forming a monocycle or a condensed ring heterocycle. Represents These heterocycles may have a substituent, and * represents a position bonded to Time. Z ₁ and Z
_The heterocycle formed by ₂ is more preferably a 5-membered to 8-membered heterocycle containing at least one of nitrogen, oxygen, sulfur and selenium as a heteroatom, and most preferably a 5-membered or 6-membered heterocycle. It is a ring.

Examples of the heterocycle represented by Z ₁ include azoles (tetrazole, 1,2,4-triazole, 1,2,3-triazole, 1,3,4-thiadiazole, 1,3,4 -Oxadiazole, 1,3-thiazole, 1,3-oxazole, imidazole, benzothiazole, benzoxazole, benzimidazole, pyrrole, pyrazole, indazole), azaindenes (terorazaindene, pentazaindene, triazaindene) , Azines (pyrimidine, triazine, pyrazine, pyridazine).

Examples of the hetero ring represented by Z ₂ include, for example, triazoles (1,2,4-triazole, benzotriazole, 1,2,3-triazole), indazole, benzimidazole, azaindenes (tetrazaindene). , Pentazaindene), and tetrazole.

Preferred substituents contained in the development inhibitor represented by (Chemical Formula 32) and (Chemical Formula 33) are as follows.
4) is mentioned.

[0093]

[Chemical 34] Here, R ₇₇ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₈ , R ₇₉ and R ₈₀ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. R ₇₇ , R ₇₈ in one molecule,
When two or more R ₇₉ and R ₈₀ are present, they may be linked to form a ring (for example, a benzene ring).

Examples of the compound represented by the chemical formula 32 include, for example, substituted or unsubstituted mercaptoazoles (for example, 1-phenyl-5-mercaptotetrazole,
1-propyl-5-mercaptotetrazole, 1-butyl-5-mercaptotetrazole, 2-methylthio-5
-Mercapto-1,3,4-thiadiazole, 3-methyl-4-phenyl-5-mercapto-1,2,4-triazole, 1- (4-ethylcarbamoylphenyl)-
2-mercaptoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-
Mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-phenyl-5-mercapto-1,3
4-oxadiazole, 1- {3- (3-methylureido) phenyl} -5-mercaptotetrazole, 1-
(4-Nitrophenyl) -5-mercaptotetrazole, 5- (2-ethylhexanoylamino) -2-mercaptobenzimidazole), substituted or unsubstituted mercaptoazaindenes (for example, 6-methyl-4-mercapto- 1,3,3a, 7-tetraazaindene,
4,6-Dimethyl-2-mercapto-1,3,3a, 7
-Tetraazaindene), substituted or unsubstituted mercaptopyrimidines (for example, 2-mercaptopyrimidine,
2-mercapto-4-methyl-6-hydroxypyrimidine).

Examples of the heterocyclic compound capable of forming imino silver include substituted or unsubstituted triazoles (eg, 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5 -Bromobenzotriazole, 5-n
-Butylbenzotriazole, 5,6-dimethylhenzotriazole), substituted or unsubstituted indazoles (eg, indazole, 5-nitroindazole, 3-
Examples thereof include nitroindazole, 3-chloro-5-nitroindazole) and substituted or unsubstituted benzimidazoles (for example, 5-nitrobenzimidazole and 5,6-dichlorobenzimidazole).

X is released from Time of the general formula (F) to become a compound having a development inhibitory property,
Further, it may be a compound which undergoes a certain chemical reaction with the developer component to have substantially no development inhibitory property or is converted into a compound having a significantly reduced amount. Examples of the functional group that undergoes such a chemical reaction include ester, carbonyl, imino, immonium, Michael addition accepting group,
Alternatively, imide may be mentioned.

Examples of such a deactivating type development inhibitor include, for example, US Pat.
0-218644, 60-221750, 60
No. 233650, or the development inhibitor residues described in No. 61-11743.

Of these, those having an ester group are particularly preferable. Specifically, for example, 1- (3-phenoxycarbonylphenyl) -5-mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) -5-
Mercaptotetrazole, 1- (3-maleinimidophenyl) -5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5- (4-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3 ，
4-thiadiazole, 5-nitro-3-phenoxycarbonylimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 1- (4-benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-methane Sulfonylethoxycarbonyl)
2-mercaptobenzothiazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl) -5-mercaptotetrazole, 5-succinimidomethylbenzotriazole, 2- {4-succinimidophenyl} -5-mercapto- 1,3,4-
Oxadiazole, 6-phenoxycarbonyl-2-mercaptobenzoxazole, 2- (1-methoxycarbonylethylthio) -5-mercapto-1,3,4-thiadiazole, 2-butoxycarbonylmethoxycarbonylmethylthio-5-mercapto- 1,3,4-thiadiazole, 2- (N-hexylcarbamoylmethoxycarbonylmethylthio) -5-mercapto-1,3,4-
Examples thereof include thiadiazole and 5-butoxycarbonylmethoxycarbonylbenzotriazole.

Of the compounds represented by the general formula (F),
The compounds represented by the following general formulas (G) and (H) are more preferable.

General formula (G)

[0101]

[Chemical 35] In the formula, R ³¹ to R ³³ are a hydrogen atom or a group capable of substituting for a hydroquinone nucleus, and P ²¹ and P ²² are a hydrogen atom or a protective group capable of being deprotected during development processing. Time, X and t have the same meanings as in formula (F).

General formula (H)

[0103]

[Chemical 36] In the formula, R ³¹ represents aryl, heterocycle, alkyl, aralkyl, alkenyl or alkynyl, and P ³¹ and P ³²
Is a hydrogen atom or a protecting group that can be deprotected during development processing. G, Time, X and t have the same meanings as in the general formula (F).

[0104] When the formula will be described in more detail (G), as the substituents R ²¹ to represented by R ^23, for example, those described as a substituent A in the general formula (F) are mentioned, R ²² and R ²³ is preferably a hydrogen atom, alkylthio, arylthio, alkoxy, aryloxy,
Amide, sulfonamide, alkoxycarbonylamino and ureido are more preferable, and hydrogen atom, alkylthio, alkoxy, amide, sulfonamide, alkoxycarbonylamino and ureido are more preferable.

R ²¹ is preferably a hydrogen atom, carbamoyl, alkoxycarbonyl, sulfamoyl, sulfonyl, cyano, acyl or a heterocyclic group, more preferably a hydrogen atom, carbamoyl, alkoxycarbonyl,
Sulfamoyl and cyano. R ²² and R ²³ may combine together to form a ring.

Examples of the protective group for P ²¹ and P ²² include those mentioned as the protective group for the hydroxyl group of A in the general formula (F), preferably acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl and imidoyl. , Oxazolyl, hydrolyzable groups of sulfonyl groups, precursor groups of the type utilizing the reverse Michael reaction described in US Pat. No. 4,009,029, US Pat. No. 4,310,
No. 612, a precursor group of a type utilizing an anion generated after the ring opening reaction as an intramolecular nucleophilic group, U.S. Pat. Nos. 3,674,478, 3,932,480 or 3,993. Precursor group that causes the anion described in US Pat. No. 661 to undergo electron transfer through a conjugated system, thereby causing a cleavage reaction, and the cleavage reaction by electron transfer of the reacted anion after ring cleavage described in US Pat. No. 4,335,200. Precursor group to wake up or US Pat. No. 4,3
Precursor groups utilizing an imidomethyl group described in Nos. 63,865 and 4,410,618 are mentioned.

P ²¹ and P ²² are preferably hydrogen atoms.

Preferred as X are mercaptoazoles and benzotriazoles. As the mercaptoazole, mercaptotetrazoles, 5-mercapto-1,3,4-thiadiazoles and 5-mercapto-1,3,4-oxadiazoles are more preferable.

Most preferably X is 5-mercapto-
1,3,4-thiadiazoles.

Of the general formula (G), the following general formula (I)
And (J).

General formula (I)

[0112]

[Chemical 37] General formula (J)

[0113]

[Chemical 38] Here, R ⁴² represents an aliphatic, aromatic or hetero ring, and M ⁴²
Represents (Chemical Formula 22).

[0114]

[Chemical Formula 39] R ⁴⁴ , R ⁴⁵ and R ⁵⁴ represent a hydrogen atom, an alkyl group or an aryl group.

L is a divalent linking group necessary for forming a 5-membered to 7-membered ring. R ⁴¹ and R ⁵¹ are R ²¹ of the general formula (G), R ⁴³ is R ²³ of the general formula (G), and − (Time) _t −
X has the same meaning as-(Time) _t -X in formula (G). Furthermore, when R ⁴² is described in detail, the aliphatic group of R ⁴² is a linear, branched, or cyclic alkyl group, alkenyl group, or alkynyl group having 1 to 30 carbon atoms. The aromatic group has 6 to 30 carbon atoms and includes a phenyl group and a naphthyl group. As the heterocycle, nitrogen, oxygen,
It is a 3- to 12-membered one containing at least one of sulfur. These may be further substituted with the groups described for the substituent of A.

The general formula (H) will be described in more detail.

The arule group represented by R ³¹ has 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group is a 5- to 7-membered group containing at least one of nitrogen, oxygen and sulfur, and examples thereof include furyl and pyridyl. The alkyl group has 1 to 30 carbon atoms, and examples thereof include methyl, hexyl and octadecyl. The aralkyl group has a carbon number of 7 to 30, and examples thereof include benzyl and trityl. The alkenyl group has 2 to 30 carbon atoms.
Examples thereof include allyl. The alkynyl group has 2 to 30 carbon atoms, and examples thereof include propargyl. R ³¹ is preferably an aryl group, more preferably phenyl.

Examples of the protecting group for P ³¹ and P ³² include those mentioned as the protecting group for the amino group represented by A in the general formula (F). R ³¹ and R ³² are preferably hydrogen atoms. G is preferably -CO-, and X is preferably the one described in the general formula (G).

R ²¹ to R ^{23 in} the general formula (G) and R ^{31 in the} general formula (H) may be substituted with a substituent. The substituent may have a so-called ballast group or a silver halide adsorbing group for imparting diffusion resistance, but it is more preferably a ballast group. When R ³¹ is a phenyl group, the substituent is preferably an electron-donating group, and examples thereof include sulfonamide, amide, alkoxy and ureido. Further, when R ²¹ , R ²² , R ²³ or R ³¹ has a ballast group, it is particularly preferable that it has a polar group such as a hydroxyl group, a carboxyl group or a sulfo group in the molecule.

In order to more specifically arrange the contents of the present invention, specific examples of the compound represented by formula (F) are shown below, but the compounds usable in the present invention are not limited to these.

[0121]

[Chemical 40]

[0122]

[Chemical 41]

[0123]

[Chemical 42]

[0124]

[Chemical 43]

[0125]

[Chemical 44]

[0126]

[Chemical formula 45]

[0127]

[Chemical formula 46]

[0128]

[Chemical 47]

[0129]

[Chemical 48]

[0130]

[Chemical 49]

[0131]

[Chemical 50]

[0132]

[Chemical 51]

[0133]

[Chemical 52]

[0134]

[Chemical 53]

[0135]

[Chemical 54]

[0136]

[Chemical 55]

[0137]

[Chemical 56]

[0138]

[Chemical 57]

[0139]

[Chemical 58]

[0140]

[Chemical 59]

[0141]

[Chemical 60]

[0142]

[Chemical formula 61]

[0143]

[Chemical formula 62]

[0144]

[Chemical formula 63]

[0145]

[Chemical 64]

[0146]

[Chemical 65]

[0147]

[Chemical formula 66]

[0148]

[Chemical formula 67]

[0149]

[Chemical 68]

[0150]

[Chemical 69]

[0151]

[Chemical 70]

[0152]

[Chemical 71] The compound represented by formula (F) of the present invention is disclosed in
-129536, 52-57828, 60-2
No. 1044, No. 60-233642, No. 60-233
No. 648, No. 61-18946, No. 61-15604.
No. 3, No. 61-213847, No. 61-230135
No. 61-236549, No. 62-62352,
62-103639, U.S. Pat. No. 3,379,52.
No. 9, No. 3,620,746, No. 4,332,828
No. 4,377,634, No. 4,684,604 and the like.

The compound represented by formula (F) may be added to any emulsion layer and / or non-photosensitive layer. It may be added to both. The addition amount is preferably 0.001 to 0.2 mmol / m ² , and more preferably 0.01 to 0.1 mmol / m ² .

The compound represented by formula (F) of the present invention can be introduced into a color light-sensitive material by various known dispersion methods.

In the oil-in-water dispersion method, an organic solvent having a low boiling point (eg, ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol) is used to apply the fine dispersion, and a substantially low boiling point organic solvent is applied to the dry film. A method in which the solvent does not remain may be used. When a high-boiling organic solvent is used, any of those having a boiling point of 175 ° C. or higher under normal pressure may be used, and one kind or two or more kinds may be arbitrarily mixed and used. The ratio of the coupler of the present invention to these high boiling point organic solvents can be in a wide range, but is in the range of 5.0 or less by weight per 1 g of the coupler. It is preferably 0 to 2.0, and more preferably 0.01 to 1.0.

The latex dispersion method described below can also be applied.

Further, various couplers and compounds described later can be mixed or used together.

The cyan, magenta and yellow coupler dispersions used in the present invention have a boiling point of 1 at a ratio represented by the following formula.
A high boiling point organic solvent having a temperature of 50 ° C. or higher can be included.

0 ≦ high-boiling point organic solvent (weight) / coupler (weight) ≦ 1.0 This ratio is preferably 0.7 or less, more preferably 0.5 or less, in view of the requirements for improving sharpness and film strength. is there.

The high boiling point organic solvent in the above formula is one which is co-emulsified.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light. In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

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

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as usual.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity 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 (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of.

Further, as described in JP-B-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. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange 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 silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

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. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
Nos. 63-89850 and BL, G
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), page 648, ibid. Thirty
7105 (Nov. 1989), pp. 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemieet.
Phisique Photographique, P
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
Press, 1964) and the like.

Monodisperse emulsions are described in US Pat. No. 3,574,62
No. 8, 3,655,394 and US Pat. Nos. 1,4.
It can be prepared by the method described in No. 13,748.

Tabular grains are described by Gatov in Photographic Science and Engineering (Gut
off, Photographic Science
and Engineering), Volume 14, 248-
257 (1970); U.S. Pat. No. 4,434,22.
No. 6, No. 4,414, 310, No. 4,433, 048
No. 4,439,520 and British Patent No. 2,11.
It can be easily prepared by the method described in No. 2,157.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and the same No. No. 307105, and the relevant parts are summarized in the table below.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
The thickness is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains are preferable.

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

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

The silver coating amount of the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

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.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, to page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention 24 to 25 pages 649 right column 868 to 870 Agents and stabilizers 6. Light absorber, pages 25 to 26, page 649, right column, page 873, filter to page 650, left column, dye, ultraviolet absorber 7. Stain, page 25, right column, page 650, left column, page 872, inhibitor-right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener, page 26, page 651, left column, pages 874-875 10. Binder page 26 page 651 left column page 873-874 11. Plasticizer, page 27, page 650, right column, page 876, lubricant 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 right column 876 to 877 inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

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

The light-sensitive material of the present invention can be prepared by the method described in JP-A-1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

International Publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 be contained.

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

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

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Further, JP-A 64-553 and 64-5.
54, 64-555 and 64-556, and pyrazoloazole couplers described in US Pat. No. 4,818,
The imidazole coupler described in No. 672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

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

Colored couplers for correcting unwanted absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD1 above.
7643, Item VII-F and No. 307105, VII
Patents described in section F, JP-A-57-151944
No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

R. D. No. 11449 and 2424
1, the bleaching accelerator releasing coupler described in JP-A-61-2201247 is effective for shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when added to the material.

A coupler capable of releasing a nucleating agent or a development accelerator imagewise during development is described in British Patent No. 2,093.
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. In addition, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1
Compounds which release a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in 45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. , A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Examples thereof include releasing couplers.

The compounds and couplers used in the present invention are
It can be incorporated into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher 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), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridodecylphosphate, tributoxyethylphosphate, trichloropropylphosphate, di-2-ethylhexylphenylphosphonate),
Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (N, N-diethyldodecaneamide, N, N-diethyllaurylamide,
N-tetradecylpyrrolidone), alcohols or phenols (isostearyl alcohol, 2,4-di-
tert-amylphenol), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivative (N, N-dibutyl-2) -Butoxy-5-
tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

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

In the color light-sensitive material of the present invention, phenethyl alcohol, or JP-A Nos. 63-257747 and 62-62 are used.
No. 272248, and 1,2-benzisothiazolin-3-one-, n-butyl p-hydroxybenzoate, phenol, 4-described in JP-A No. 1-80941.
It is preferable to add various preservatives or antifungal agents such as chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

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

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more 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 a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een) and others in Photographic Science and Engineering (Photogr. Sci. E.
ng. ), Vol. 19, No. 2, pp. 124-129, can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached at that time is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

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

The photographic material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred. The color photographic light-sensitive material according to the present invention has the RD. No. 17643 28-29
Page, ibid. 18716, 651 left column to right column, and the same No. Development processing can be performed by a usual method described on pages 880 to 881 of 307105.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline and their sulphates, nitrates or p-toluenesulphonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzothiazole compound or a mercapto compound. It is common to include such development inhibitors or antifoggants. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, 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, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine 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 representative examples.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, 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. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 31 or less per square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenisher. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82 is available.
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The time of 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 a color developing agent. it can.

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

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129;
JP-B-45-8506, JP-A-52-20832,
53-32735, U.S. Pat. No. 3,706,561.
Derivatives described in Japanese Patent No. 1,127,7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,43.
Polyoxyethylene compounds described in No. 0; JP-B-45
Polyamine compounds described in JP-A-8836;
9-40,943, 49-59,644, 53
-94,927, 54-35,727, 55-
26,506 and 58-163,940; bromide ions and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of having a large accelerating effect, and in particular, US Pat. No. 3,893,85
No. 8, West German Patent No. 1,290,812, JP-A-53-
The compounds described in No. 95,630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain, in addition to the above compounds. Particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid and hydroxyacetic acid are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

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

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

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage counterflow method is described in the Journal of the Societ.
y of Motion Picture and Te
le-vision Engineers Volume 64,
P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved by a method disclosed in JP-A-62-288,838.
The method of reducing calcium ion and magnesium ion described in No. 10 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". Chemistry "(1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Microbial and Antifungal Encyclopedia" (1986) Can also be used.

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

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

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

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

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Research Disclosure No. 14, 850 and the same No. Examples of the Schiff base type compounds described in JP-A No. 15,159, 15, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A No. 53-135628. be able to.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64399 and JP-A-57-14.
Nos. 4547 and 58-115438.

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

The silver halide light-sensitive material of the present invention is described in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, No. 59-218443, No. 61-23805.
It is also applicable to the photothermographic materials described in No. 6, European Patent No. 210,660A2, and the like.

[0228]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. (Preparation of Emulsion) [Preparation of Emulsion] Various silver iodobromide emulsions were prepared as follows. (1) Preparation of R-1 to 4 emulsions A 3.0% by weight gelatin solution whose temperature was kept at 60 ° C.
NH ₄ OH was added to 0 liter to adjust the pH to 10.3. To this solution, 42 cc each of 0.5 M silver nitrate solution and 0.5 M potassium bromide solution were added by the double jet method over 2 minutes. After keeping for 10 minutes, 100 cc of 1.0 M silver nitrate solution was slowly added, and then the pH was returned to the original value, and in 60 minutes, a silver nitrate aqueous solution containing 130 g of silver nitrate and a potassium bromide aqueous solution containing 1.7 g of potassium iodide were added. Added at constant flow rate. During this period, pBr was kept at 2.90. Further, an aqueous silver nitrate solution containing 20 g of silver nitrate and an aqueous potassium bromide solution were added at a constant flow rate for 10 minutes while keeping pBr at 2.85. After that, the emulsion was desalted by a conventional flocculation method and pH = 6.
After adjusting to 5, pAg = 8.5, it was optimally chemically sensitized with sodium thiosulfate, potassium chloroaurate and potassium thiocyanate. In this way, the diameter when converted to a sphere is 1 μm,
An emulsion having an AgI content of 1.0 mol% was obtained. Similarly, the temperature during grain formation and the amount of potassium iodide were changed, and spectral sensitization was performed to prepare R-1 to 4 emulsions.

The spectral sensitization of these emulsions was carried out as follows.

In preparing a blue-sensitive emulsion, spectral sensitizing dyes S-6 and S-7 were added before chemical sensitization, and the amounts shown in Table 1 below were added. When preparing a green-sensitive emulsion, spectral sensitizing dyes S-4, S-5 and S-9 were added after the completion of chemical sensitization.
In preparing a red-sensitive emulsion, spectral sensitizing dyes S-2, S-3, and S-8 were added after chemical sensitization. (2) Preparation of M-1 to 4 emulsions To 1.0 liter of a 1.0% by weight gelatin solution containing 0.10 M potassium bromide, which was kept at a temperature of 60 ° C., while stirring it, 0 by the double jet method was used. 42 cc of each of 0.5 M silver nitrate solution and 0.5 M potassium bromide solution was added for 30 seconds. After that, 1.0M silver nitrate solution 10
Slowly add 0 cc, then add NH ₄ OH and p
After maintaining at H = 9.3 for 20 minutes, the pH was returned to the original value, and further, over 60 minutes, an aqueous solution of silver nitrate containing 130 g of silver nitrate and an aqueous solution of potassium bromide containing 1.7 g of potassium iodide were added at a constant flow rate. During this period, pBr was kept at 2.35. Further, an aqueous silver nitrate solution containing 20 g of silver nitrate and an aqueous potassium bromide solution were added at a constant flow rate for 10 minutes while maintaining pBr at 2.55. Thereafter, the emulsion was desalted by a conventional flocculation method to obtain pH = 6.5, pAg at 40 ° C.
= 8.5 and then optimally chemically sensitized with sodium thiosulfate, potassium chloroaurate and potassium thiocyanate. Thus, an emulsion having a sphere-converted diameter of 1 μm and an AgI content of 1.0 mol% was obtained. Similarly, the temperature at the time of grain formation, the amount of potassium iodide and the grain formation potential were changed, and (1)
Spectral sensitization was carried out in the same manner as above to prepare M-1 to 3 emulsions. (3) Preparation of T-1 to 4 emulsions To 1.0 liter of 1.0 wt% gelatin aqueous solution containing 0.08 M potassium bromide, while stirring it, 0.5 M silver nitrate aqueous solution and 0 by a double jet method were prepared. 42 cc of a 0.5 M aqueous solution of potassium bromide was added over 25 seconds. During this time, the temperature was kept at 40 ° C. After the addition, 14 g of gelatin was added and the temperature was raised to 75 ° C. Then, 100 cc of 1.0 M silver nitrate aqueous solution was slowly added, and NH ₄ OH was further added to maintain pH = 9.3 for 20 minutes, and then the pH was returned to the original value, and 130 g was added in 60 minutes.
The silver nitrate aqueous solution containing silver nitrate and the potassium bromide aqueous solution containing 1.7 g of potassium iodide were added at an accelerated flow rate (the flow rate at the end was 19 times that at the start). During this period, pBr is 2.
Was kept at 35. Further, for 10 minutes, an aqueous solution of silver nitrate containing 20 g of silver nitrate and an aqueous solution of potassium bromide were added to have a pBr of 2.5.
While maintaining at 5, the flow rate was accelerated (the flow rate at the end was 5 times that at the start). After that, the emulsion was desalted by a conventional flocculation method to obtain a pH of 6.5 at 40 ° C.
After being adjusted to Ag = 8.5, it was optimally chemically sensitized with sodium thiosulfate, potassium chloroaurate and potassium thiocyanate. In this way, the diameter converted to sphere is 1 μm, AgI
An emulsion having a content of 1.0 mol% was obtained. Similarly, the temperature at the time of grain formation, the amount of potassium iodide and the grain formation potential were changed to obtain T
-1 to 4 emulsions were prepared. Spectral sensitization was performed as in (1).

In all the emulsions, tabular grains accounted for 98% or more of the projected area of all grains having a projected area equivalent to a circle of 0.2 μm or more. (4) Preparation of V-1 to 4 emulsions 4 cc of the polymer P-1 of the present invention was added to 1.0 liter of a 4.0% by weight gelatin aqueous solution containing 0.04 M potassium bromide, and the mixture was kept at 45 ° C. to pH. Was set to 1.85.
While stirring, 0.5M silver nitrate aqueous solution and 0.5M potassium bromide aqueous solution were pA for 50 seconds by the double jet method.
42 cc was added while keeping g at 9.7. p
After adjusting Ag to 9.8, the temperature was raised to 60 ° C., 14 cc of 0.8 N ammonium sulfate was added, and then the pH was adjusted to 10.0 with NaOH. After 10 minutes,
100 g gelatin and 0.1 cc PLURONIC ^™
The pAg was adjusted to 9.2 and the pH was adjusted to 5.8 with an aqueous solution containing 31R1 in 1 liter. 130 g
The silver nitrate aqueous solution containing silver nitrate and the potassium bromide aqueous solution containing 1.7 g of potassium iodide were added at an accelerated flow rate (the flow rate at the end was 19 times that at the start). During this period, pAg was 9.
It was kept at 2. Further, in 10 minutes, the silver nitrate aqueous solution containing 20 g of silver nitrate and the potassium bromide aqueous solution were adjusted to pBr of 2.55.
Was added at an accelerated flow rate (the flow rate at the end was 5 times that at the start). After that, the emulsion was desalted by a conventional flocculation method to obtain pH = 6.5, pA at 40 ° C.
After adjusting to g = 8.5, optimum chemical sensitization was carried out with sodium thiosulfate, potassium auronate and potassium thiocyanate. Thus, an emulsion having a sphere-converted diameter of 1 μm and an AgI content of 1.0 mol% was obtained. Similarly, the temperature at the time of grain formation, the amount of potassium iodide and the grain formation potential were changed, and (1)
Spectral sensitization was carried out in the same manner as above to prepare V-1 to 4 emulsions.
In each emulsion, the projected area has a circle-converted diameter of 0.2.
Over 98% of the projected area of all grains of .mu.m or larger was occupied by tabular grains.

The sensitivity between the above emulsions was higher as the size was larger.

The silver iodobromide emulsion grains used in the examples are shown in Table 3. Table 3 Particle name Particle characteristics Particle conversion Fluctuation AgI average Particle average particle diameter Coefficient Content Aspect ratio Structure (μm) (%) (%) R-1 Cube monodisperse 1.0 11 3.7-Yes R-2 Cube monodisperse 0.5 9 3.5-Yes R-3 Cube monodisperse 0.3 7 2.8-Yes R-4 Cube monodisperse 0.5 7 2.8-Yes M-1 polydisperse flat plate 1. 0 30 3.0 8.5 Yes M-2 polydisperse flat plate 0.5 20 5.0 5.0 4.5 Yes M-3 polydisperse flat plate 0.6 22 1.3 7.6 Yes M-4 polydisperse flat plate 1 .1 30 1.3 10.2 Yes T-1 monodisperse flat plate 1.0 10 3.0 8.8 Yes T-2 monodisperse flat plate 0.5 9 5.0 4.2 Yes T-3 monodisperse flat plate 0.6 9 1.3 8.0 Yes T-4 monodisperse flat plate 1.1 10 1.3 10.0 Yes V-1 monodisperse flat plate 1.0 8 3.0 8. 4 Yes V-2 monodisperse flat plate 0.5 7 5.0 4.5 Yes V-3 monodisperse flat plate 0.6 7 1.3 7.2 Yes V-4 monodisperse flat plate 1.1 8 1.3 9. .8 Yes Table 4 AgXlmol layer name Emulsion name Addition amount per sensitizing dye (g) Fourth layer R-1 S-2 / S-3 / S-8 0.025 / 0.25 / 0.01 R-2 S-2 / S -3 / S-8 0.025 / 0.25 / 0.01 5th layer R-1 S-2 / S-3 / S-8 0.025 / 0.25 / 0.01 M-2 S-1 / S-3 / S-8 0.035 / 0.40 /0.02 6th layer M-1 S-2 / S-3 / S-8 0.055 / 0.50 / 0.03 M-2 S-1 / S-3 / S-8 0.035 / 0.40 / 0.02 9th layer R-1 S -4 / S-5 0.25 / 0.05 R-2 S-4 / S-5 0.50 / 0.10 10th layer R-1 S-4 / S-5 0.25 / 0.05 11th layer M-1 S-4 / S- 5 / S-9 0.30 / 0.07 / 0.10 15th layer R-3 S-6 / S-7 0.06 / 0.22 R-4 S-6 / S-7 0.05 / 0.20 M-3 S-6 / S- 7 0.04 / 0.15 16th layer M-4 S-6 / S-7 0.04 / 0.15 M-4 S-6 / S-7 0.06 / 0.22 17th layer M-4 S-6 / S-7 0.06 / 0.22 ( Example 1) Preparation of Sample 101 Sample 101 was prepared by preparing a multilayer color light-sensitive material composed of each layer having the following composition on a 127 μm thick cellulose triacetate film support having an undercoat. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-2 0.1 g UV absorber U-3 0.1 g UV absorber U-4 0.1 g Ultraviolet absorber U-5 0.1 g High boiling point organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g Second layer: intermediate layer Gelatin 0.40 g High boiling point Organic solvent Oil-3 0.1 g Dye D-4 0.4 mg Third layer: intermediate layer Fine grained silver iodobromide emulsion (average grain size 0.06 μm, variation coefficient 18%, Agl content) 1 mol%) Silver amount 0.05 g Gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion R-1 Silver amount 0.1 g Emulsion R-2 Silver amount 0.4 g Finely fogged internal iodobromide Silver emulsion (average grain size 0.06μm, fluctuation Number 18%, Agl content 1 mol%) Silver amount 0.05 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-3 0.05 g Coupler C-9 0.05 g Coupler C -6 0.02 g High-boiling-point organic solvent Oil-2 0.1 g Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion R-1 Silver amount 0.2 g Emulsion M-2 Silver amount 0.3 g Internally fogged fine grain iodine Silver bromide emulsion (average grain size 0.06 μm, coefficient of variation 18%, Agl content 1 mol%) silver amount 0.05 g gelatin 0.8 g coupler C-1 0.2 g coupler C-2 0.05 g coupler C- 3 0.2 g Coupler C-9 0.05 g Coupler C-10 0.01 g High boiling point organic solvent Oil-2 0.1 g Sixth layer: high-sensitivity red-sensitive emulsion layer Emulsion M-1 Silver amount 0.4 g Emulsion M- 2 0.1 g gelatin 1 1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Coupler C-9 0.1 g Additive P-1 0.1 g Seventh layer: Intermediate layer Gelatin 0.6 g Additive P -0.3 g Mixing inhibitor Cpd-I 2.6 mg Ultraviolet absorber U-1 0.1 g Ultraviolet absorber U-5 0.1 g Dye D-1 0.02 g Eighth layer: Intermediate layer Surface and inside Fogging silver iodobromide emulsion (average grain size 0.06 μm, coefficient of variation 16%, Agl content 0.3 mol%) silver amount 0.02 g gelatin 1.0 g additive P-1 0.2 g anti-mixing agent Cpd -C 0.1g Anti-mixing agent Cpd-L 0.1g 9th layer: Low-sensitivity green-sensitive emulsion layer Emulsion R-1 Silver amount 0.2g Emulsion R-2 Silver amount 0.3g Surface and inner fine particles Silver iodobromide emulsion (average grain size 0.06 μm, coefficient of variation 18%, gl content 1 mol%) Silver amount 0.05 g Gelatin 0.5 g Coupler C-4 0.05 g Coupler C-7 0.05 g Coupler C-8 0.10 g Coupler C-11 0.10 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-L 0.02 g High boiling point organic solvent Oil-1 0.1 g High boiling point organic solvent Oil-2 0.1 g Tenth Layer: Medium-speed green-sensitive emulsion layer Emulsion R-1 Silver amount 0.4 g Fine grained silver iodobromide emulsion with surface and inside fogged (average grain size 0.06 μm, variation coefficient 18%, Agl content 1 mol%) Silver amount 0.05 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-8 0.1 g Coupler C-11 0.05 g Compound Cpd-B 0. 3g Compound Cpd-D 0.02g Compound Cpd-F 0.02g Compound Cpd-G 0.05g Compound Cpd-L 0.05g High boiling organic solvent Oil-2 0.01g Layer 11: High sensitivity green sensitive emulsion layer Emulsion M-1 Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.1 g Coupler C-7 0.1 g Coupler C-8 0.1 g Coupler C-11 0.1 g Compound Cpd-B 0.08 g Compound Cpd- E 0.02g Compound Cpd-F 0.02g Compound Cpd-G 0.02g Compound Cpd-L 0.02g High boiling point organic solvent Oil-1 0.02g High boiling point organic solvent Oil-2 0.02g 12th layer: Intermediate Layer Gelatin 0.6 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.07 g 13th layer: Yellow filter layer Yellow colloidal silver Silver 0.07 g Gelatin 1.1 g Color-mixing inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g 14th layer: Intermediate layer Gelatin 0.6 g 15 layers: low-sensitivity blue-sensitive emulsion layer Emulsion R-3 Silver amount 0.2 g Emulsion R-4 Silver amount 0.3 g Emulsion M-3 Silver amount 0.1 g Finely grained silver iodobromide emulsion (average grain) Diameter 0.06 μm, coefficient of variation 18%, Agl content 1 mol%) Silver amount 0.05 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.2 g Coupler C-10 0.4 g 16th layer : Medium sensitivity blue-sensitive emulsion layer Emulsion M-3 Silver amount 0.1 g Emulsion M-4 Silver amount 0.4 g Fine grained silver iodobromide emulsion with surface and inside fogged (average grain size 0.06 μm, variation coefficient 18) %, Ag1 content 1 mol%) Silver amount 0.05 g Ze Ratin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.1 g Coupler C-10 0.1 g 17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion M-4 Silver amount 0.4 g Gelatin 1.2 g Coupler C -5 0.1 g Coupler C-6 0.6 g Coupler C-10 0.1 g 18th layer: 1st protective layer Gelatin 0.7 g UV absorber U-1 0.04 g UV absorber U-2 0.01 g UV Absorber U-3 0.03 g Ultraviolet absorber U-4 0.03 g Ultraviolet absorber U-5 0.05 g Ultraviolet absorber U-6 0.05 g High boiling organic solvent Oil-1 0.02 g Formalin scavenger Cpd-H 0.4 g Dye D-3 0.05 g Compound Cpd-A 0.02 g 19th layer: second protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI 1 mol%) Silver amount 0.1 mg Gelatin 0.4 g 20th layer: Third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μm) 0.1 g Methylmethacrylate and acrylic acid 4: 6 Copolymer (average particle size 1.5 μm) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g In addition, the above composition is used for all emulsion layers. Additive F-
1-F-8 were added. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer and used.

Further, as an antiseptic and antifungal agent, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol were added.

The structural formulas of the compounds used in Sample 101 are shown below.

[0237]

[Chemical 72]

[0238]

[Chemical formula 73]

[0239]

[Chemical 74]

[0240]

[Chemical 75]

[0241]

[Chemical 76]

[0242]

[Chemical 77]

[0243]

[Chemical 78]

[0244]

[Chemical 79]

[0245]

[Chemical 80]

[0246]

[Chemical 81]

[0247]

[Chemical formula 82]

[0248]

[Chemical 83]

[0249]

[Chemical 84]

[0250]

[Chemical 85] (Preparation of Sample 102) Sample 101 was prepared in the same manner as in Sample 101, except that the DIR compound I-50 of the present invention was added to the 13th layer in an amount of 15 mg / m ² . I-50 was used by dissolving it in 0.1 times the amount of dioctylhydroquinone in 4 times the amount of trinonyl phosphate, adding W-3, emulsifying and dispersing with a homogenizer, and then adding it. All the compounds of the present invention were used by emulsifying and dispersing in the same manner. (Preparation of Sample 103) Compound I-5 in Sample 102
It was prepared in the same manner except that I-45 was added at 30 mg / m ² instead of 0. (Preparation of Samples 104 to 106) First in Sample 101
Emulsion M-3 of 5 to 17 layers was added to T-3, and M-4 was added to T-4.
Samples 101 to 103 were prepared in the same manner except that (Preparation of Samples 107 to 110) First in Sample 105
It was prepared in the same manner as in Sample 105, except that the three layers of the DIR compound were replaced with the compounds shown in Table 5 below in equimolar amounts. (Preparation of Samples 111 to 116) In Samples 105 to 110, the emulsions T-3 and T-4 of the 15th to 17th layers were changed to V-3,
It was created in the same manner as Samples 105 to 110, except that it was replaced with V-4. (Preparation of Sample 201) Sample 101 was prepared in the same manner as in Sample 101, except that the DIR compound I-50 of the present invention was added to the second layer in an amount of 15 mg / m ² .
It was dissolved in 1-fold amount of dioctylhydroquinone in 4-fold amount of trinonyl phosphate, added with W-3 as an emulsifier, emulsified and dispersed by a homogenizer, and then added. All the compounds of the present invention were used by emulsifying and dispersing in the same manner. (Preparation of sample 202) Compound I-5 in sample 201
It was prepared in the same manner except that I-45 was added at 30 mg / m ² instead of 0. (Preparation of Samples 203 to 205) Samples 101, 201, 2
No. 02, the fourth to sixth layers of emulsion grains M-2 were added to T-2.
In the same manner, except that M-1 was replaced with T-1. (Preparation of Samples 206 to 209) First in Sample 205
It was prepared in the same manner as in Sample 205, except that the DIR compounds in the three layers were replaced with the compounds shown in Table 5 below in equimolar amounts. (Preparation of Samples 210 to 215) In Samples 204 to 209, emulsions T-2 and T-1 of the fourth to sixth layers were replaced with V-2 and V-.
It was created in the same manner as Samples 204 to 209 except that it was replaced with 1. (Preparation of Sample 301) Sample 101 was prepared in the same manner as in Sample 101, except that 10 mg / m ² of DIR compound I-50 of the present invention was added to the seventh layer. I-50 is 0.
It was dissolved in 1-fold amount of dioctylhydroquinone in 4-fold amount of trinonyl phosphate, added with W-3 as an emulsifier, emulsified and dispersed by a homogenizer, and then added. All the compounds of the present invention were used by emulsifying and dispersing in the same manner. (Preparation of Sample 302) Compound I-5 in Sample 301
It was prepared in the same manner except that I-45 was added in an amount of 20 mg / m ² instead of 0. (Preparation of Samples 303 to 305) Samples 101, 201, 2
No. 02, the emulsion grains M-2 of the 9th to 11th layers were mixed with T-2.
In the same manner, except that M-1 was replaced with T-1. (Preparation of Samples 306 to 309) No. 7 in Sample 205
It was prepared in the same manner as in Sample 305 except that the DIR compound in the layer was replaced with the compounds shown in Table 5 below in an equimolar amount. (Preparation of Samples 310 to 315) In Samples 304 to 309, the emulsions T-2 and T-1 of the ninth to eleventh layers were V-2 and V, respectively.
It was created in the same manner as Samples 304 to 309, except that it was replaced with -1.

The obtained samples 101 to 315 were cut into strips, subjected to wedge exposure, and subjected to sensitometry through the following processing steps. Next, a sample that was similarly exposed to perform a sensitizing process was processed in the same process except that the first development time was 8 '. After the density measurement, the logE difference at the points giving the densities of 0.3 and 1.0 was obtained and used as the gradation of the high-ride portion. The larger this value is, the harder the gradation of the highlight part is, and if the gradation is too high, the highlight part cannot be sufficiently drawn. Further, in order to measure the sharpness, exposure was performed through an MTF pattern, and after the same treatment, measurement was carried out with a microdensitometer. The sharpness was evaluated at a spatial frequency of 10 cycles / mm.
The RMS value was measured as a measure of graininess.

The results obtained are shown in Table 4. The sample of the present invention is excellent in graininess and sharpness, and even when the sensitized development is performed, the gradation of the highlight portion of the comparative sample becomes hard, whereas the sample of the present invention has a gradation balance on the highlight side. Is almost the same as in the case of the standard development 6 ', and it has excellent sensitizing development suitability. In addition, the ISO of these samples
When the sensitivity was measured, all samples had ISO sensitivity of 100 to 120 at developing time 6'and ISO sensitivity at developing time 8 '.
It was 190-240.

Development processing step used in Example 1 Processing step Processing step Time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38 ° C. 12 liters 2.2 liter / m ² First water washing 2 minutes 38 ° C. 4 liters 7.5 liters / M ² Inversion 2 minutes 38 ° C. 4 liters 1.1 liters / m ² color development 6 minutes 38 ° C. 12 liters 2.2 liters / m ² adjustment 2 minutes 38 ° C. 4 liters 1.1 liters / m ² bleaching 6 minutes 38 ° C. 12 liters 0.22 liters / m ² fixed 4 minutes 38 ° C. 8 liters 1.1 liters / m ² second washing 4 minutes 38 ° C. 8 liters 7.5 liters / m ² stable 1 minute 25 ° C. 2 liter 1.1 liter / m ² The composition of each treatment liquid was as follows. (Black and White Development) Mother Liquor Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 2.0 g 2.0 g sodium sulfite 30 g 30 g hydroquinone potassium monosulfonate 20 g 20 g potassium carbonate 33 g 33 g 1-phenyl-4 -Methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Add water 1000 ml 1000 ml pH 9 .60 9.60 The pH was adjusted with hydrochloric acid or potassium hydroxide. (Reversal liquid) Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g Same as mother liquor Stannous chloride dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide. (Color developer) Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate 12-hydrate 36 g 36 g Bromide Potassium 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazine acid 1.5 g 1.5 g N-ethyl- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 11 g 11 g 3,6-dithia-1,8-octanediol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.80 12.00 pH was adjusted with hydrochloric acid or potassium hydroxide. (Pre-bleaching) Mother liquor Replenisher Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ Dihydrate 8.0 g 8.0 g Sodium sulfite 6.0 g 8.0 g 1-thioglycerol 0.4 g 0.4 g Formaldehyde sodium bisulfite adduct 30 g 35 g Water was added to 1000 ml pH 6.30 6.10 The pH was adjusted with hydrochloric acid or sodium hydroxide. (Bleach) Mother liquor Replenisher Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ Dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ dihydrate 120 g 240 g Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water 1000 ml 1000 ml pH 5.70 5.50 The pH was adjusted with hydrochloric acid or sodium hydroxide. (Fixer) Mother liquor Replenisher Ammonium thiosulfate 8.0 g Same sodium sulphite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 The pH was adjusted with hydrochloric acid or aqueous ammonia. (Final rinse solution) Mother liquor Replenisher 1,2, Benzisothiazolin-3-onefoliooxy 0.02g 0.03g Ethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.3g 0.3g Polymaleic acid (average molecular weight 2000) 0.1 g 0.15 g Water added 1000 ml 1000 ml pH 7.0 7.0 Table 5 Highlight gradation Experiment No Sample No DIR compound Sharpness Granularity 6'8 '1 101 (Comparative example) None 1.07 0.024 0.78 0.68 2 102 (Comparative example) 1-57 1.18 0.019 0.72 0.72 3 103 (Comparative example) 1-45 1.13 0.021 0.75 0.73 4 104 (Comparative example) None 1.03 0.022 0.70 0.83 5 105 (Invention) 1-57 1.18 0.016 0.74 0.73 6 106 (invention) 1-45 1.15 0.016 0.75 0.74 7 107 (invention) 1-70 1.18 0.017 0.77 0.75 8 108 (invention) 1-71 1.20 0.016 0.75 0.73 9 109 (invention) 1-81 1.15 0.017 0.75 0.73 10 110 (Invention) 1-64 1.15 0.015 0.77 0.75 11 105 (Invention) 1-57 1.19 0.014 0.74 0.74 12 106 (Invention) 1-45 1.16 0.014 0.75 0.74 13 107 (Invention) 1-70 1.19 0.014 0.77 0.76 14 108 (Invention) 1-71 1.22 0.013 0.75 0.74 15 109 (Invention) 1-81 1.16 0.015 0.75 0.74 16 110 (Invention) 1-64 1.17 0.015 0.77 0.75 17 101 (Comparative example) None 1.12 0.018 0.78 0.68 18 201 (Comparative example) 1-57 1.18 0.012 0.72 0.72 19 202 (Comparative example) 1-45 1.14 0.013 0.75 0.73 20 203 (Comparative example) None 1.12 0.016 0.70 0.83 21 204 (Invention) 1-57 1.19 0.010 0.74 0.73 22 205 (Invention) 1-45 1.15 0.011 0.75 0.73 23 206 (Invention) 1-70 1.18 0.010 0.77 0.75 24 207 (Invention) 1-71 1.20 0.010 0.75 0.73 25 208 (Invention) 1-81 1.15 0.011 0.75 0.73 26 209 (Invention) 1 -64 1.15 0.011 0.77 0.75 27 204 (invention) 1-57 1.17 0.008 0.74 0.74 28 205 (invention) 1-45 1.16 0.009 0.75 0.74 29 206 (invention) 1-70 1.19 0.008 0.77 0.76 30 207 (invention) ) 1-71 1.21 0.008 0.75 0.74 31 208 (invention) 1-8 1 1.17 0.009 0.75 0.74 32 209 (Invention) 1-64 1.17 0.009 0.77 0.75 33 101 (Comparative example) None 1.10 0.021 0.80 0.85 34 301 (Comparative example) 1-57 1.16 0.018 0.78 0.68 35 302 (Comparative example) 1- 45 1.13 0.020 0.72 0.75 36 303 (Comparative example) None 1.11 0.022 0.82 0.88 37 304 (Invention) 1-57 1.19 0.016 0.71 0.68 38 305 (Invention) 1-45 1.17 0.017 0.71 0.68 39 306 (Invention) 1- 70 1.18 0.015 0.72 0.68 40 307 (Invention) 1-71 1.20 0.015 0.70 0.68 41 308 (Invention) 1-81 1.17 0.015 0.73 0.70 42 309 (Invention) 1-64 1.17 0.016 0.72 0.70 43 304 (Invention) 1-57 1.21 0.015 0.71 0.71 44 305 (Invention) 1-45 1.19 0.015 0.71 0.72 45 306 (Invention) 1-70 1.20 0.013 0.72 0.71 46 307 (Invention) 1-71 1.22 0.013 0.70 0.71 47 308 (This Invention) 1-81 1.19 0.013 0.73 0.73 48 309 (Invention) 1-64 1.19 0.014 0.72 0.72 Data for the blue sensitive layer are used for Experiment Nos.
From 17 to 32, the data of the red-sensitive layer is shown in Experiment No. 33 to
Up to 48, the data of the green-sensitive layer are shown.

As the sharpness, the MTF value at a spatial frequency of 10 c / mm was obtained. Granularity is aperture diameter 48μφ
The value at the density of 1.5 measured in 1. was used. (Example 2) Monodisperse tabular emulsion grains V-1 to V- of the present invention
Polymer compound V-1 of the present invention used in the preparation of
Instead of the polymer compound P-7, P-19, P-29
Grains were prepared by substituting the same amount of the above ingredients to prepare a color sensitized emulsion. These emulsions were designated as V-1 in the above example.
~ Create a sample with equal weight replacement instead of V-4,
When the same evaluation was performed, the same effect as when V-1 to V-4 was used was obtained. (Example 3) Fourth to fifth samples 101 to 306,
Corresponding samples were prepared in the same manner as Samples 101 to 306, except that the fine grain emulsion having the inside fogged 9, 10, 15 and 16 layers and the fine grain emulsion having the surface and the inside fogged were removed. When the same experiment as in Examples 1 to 3 was performed on these, the gradation balance of the highlight portion was good, but the sharpness was lowered. Further, the ISO sensitivity when the developing time was 8'was as low as 150 to 190, and the sensitivity was not sufficient during the sensitized development. Example 4 Preparation of Sample 401 A sample 401 was prepared by preparing a multilayer color light-sensitive material having the following compositions on a cellulose triacetate film support having a thickness of 91 μm and having an undercoat.

The numbers represent the added amount (g) per m ² .
The effect of the added compound is not limited to the described use.

First Layer: Antihalation Layer Gray Colloidal Silver 0.34 Gelatin 2.40 Second Layer: Intermediate Layer Gelatin 1.20 Third Layer: Low Sensitivity Red Sensitive Emulsion Layer Emulsion A Silver Amount 0.60 Emulsion X Silver amount 0.06 Gelatin 0.90 Coupler C-1 0.20 High boiling point organic solvent Oil-1 0.10 Compound Cpd-L 0.05 Fourth layer: High-sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.50 Emulsion Y Silver amount 0.05 Gelatin 1.50 Coupler C-1 0.90 High boiling point organic solvent Oil-1 0.40 Fifth layer: Intermediate layer Gelatin 0.60 Compound Cpd-L 0.16 Dye D-10 .65 Sixth layer: Intermediate layer Gelatin 0.60 Seventh layer: Low sensitivity green sensitive emulsion layer Emulsion C Silver amount 0.45 Gelatin 0.90 Coupler C-7 0.20 Coupler C-11 0.07 High boiling organic Solvent Oil-2 11th layer: high-sensitivity green-sensitive emulsion layer Emulsion D Silver amount 0.45 Emulsion X Silver amount 0.07 Emulsion Y Silver amount 0.05 Gelatin 1.50 Coupler C-7 0.60 Coupler C-11 0. 25 High-boiling point organic solvent Oil-2 0.40 Ninth layer: Intermediate layer Gelatin 0.60 Tenth layer: Intermediate layer Gelatin 0.60 Compound Cpd-L 0.11 Dye E-2 0.27 High-boiling point organic solvent Oil -3 0.60 11th layer: Low-sensitivity blue-sensitive emulsion layer Emulsion E Silver amount 0.45 Gelatin 0.90 Coupler C-4 0.18 High boiling point organic solvent Oil-1 0.06 Compound Cpd-L 0.05 12th layer: High-sensitivity green-sensitive emulsion layer Emulsion F Silver amount 0.55 Emulsion X Silver amount 0.07 Emulsion Y Silver amount 0.05 Gelatin 2.40 Coupler C-4 1.55 High boiling point organic solvent Oil-10 .50 13th layer: 1st protective layer UV absorber -1 0.38 UV absorber U-2 0.13 Compound Cpd-L 0.07 Gelatin 1.40 14th layer: Second protective layer Gelatin 0.97 Emulsion X Silver amount 0.12 Yellow colloidal silver Silver amount 0 0.003 Gelatin hardening agent H-2 0.31 The above-mentioned couplers, compounds, and high boiling point organic solvents have the same structures as those in Example 1 with the same numbers as shown in Example 1.

The dye E-3 is represented by the following chemical formula 86.

[0258]

[Chemical 86] Oil-3 N, N-diethyllaurylamide H-2 bis (vinyl sulfone) methane emulsion is shown in Table 7 below. Table 7 Emulsion name Contents Average grain size Variation coefficient AgI content (μm) (%) (%) A Red-sensitive monodisperse tabular silver iodobromide emulsion 0.4 8 4.0 B Red-sensitive monodisperse tabular silver iodobromide Emulsion 1.0 10 4.0 C Green-sensitive monodisperse tabular silver iodobromide emulsion 0.4 9 4.0 D Green-sensitive monodisperse tabular silver iodobromide emulsion 1.2 11 4.0 E Blue-sensitive monodisperse tabular emulsion Silver iodobromide emulsion 0.5 9 3.0 F Blue-sensitive monodispersed tabular silver iodobromide emulsion 1.4 10 3.0 X Silver bromide Lippmann emulsion 0.030 Y Fine silver iodobromide emulsion 0.05 6 4.8 Preparation of Sample 402 In Sample 401, the compounds I-57, I-45, I-70, I-71, and I-80 of the present invention used in Example 1 were used as the second layer, the sixth layer, 1X10exp for 10th layer
Sample (40) was prepared in the same manner as sample 402 except that (-5) mol was added.
2 to 406 were created.

When these samples were evaluated in the same manner as in Example, sample 402 containing the compound of the present invention was added.
Like Nos. 406 to 406, in addition to the effect of improving the graininess and sharpness as in Example 1, excellent performance was obtained in terms of sensitized development characteristics.

[0260]

As is apparent from the above examples, by the combination of the present invention, the sharpness and graininess are improved, and the gradation balance upon sensitized development is good, and the object of the present invention is achieved. I know that I can do it.

Claims (5)

[Claims] 1. In a photographic light-sensitive material having a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer unit each comprising one or more emulsion layers on a support, at least one of the emulsion layers has an average aspect ratio. The average iodine of the emulsion layers containing the tabular monodisperse emulsion having a structure due to the difference in halogen composition inside two or more grains and having the highest sensitivity among at least one emulsion layer unit constituting the emulsion layer unit. The silver iodide content is less than the average silver iodide content of the other emulsion layers in the same unit, and the average silver iodide content of the photosensitive emulsion layer unit closest to the incident light side is 0 to 3 mol%.
And the average silver iodide content of the other emulsion layer units is less than or equal to, and contains at least one of the compounds represented by the following general formula (F). General formula (F) In the formula, A represents a redox mother nucleus or a precursor thereof, and is not oxidized until it is oxidized (Tim.
e) Represents an atomic group that allows _t X to leave. Time represents a group that releases X after being released from the oxidant of A, and X represents a development inhibitor. L represents a divalent linking group, and G represents a polarizable group. n, m, and t each represent 0 or 1. 2. The color photographic light-sensitive material according to claim 1, wherein the compound of the general formula (F) is contained in a substantially light-insensitive intermediate layer adjacent to the light-sensitive emulsion layer. 3. A block polymer of a hydrophobic polyalkylene oxide represented by the following general formula (I) and a hydrophilic polyalkylene oxide represented by the general formula (II) in at least one photosensitive emulsion layer. 3. The color photographic light-sensitive material according to claim 1, which further comprises a polymer having in the molecule thereof. General formula (I) General formula (II): 4. The color according to claim 1, wherein a positive image is obtained by going through a B / W development step after imagewise exposure and then performing color development. Photographic material. 5. The emulsion or colloidal silver, the surface and / or interior of which is fogged, in any one of the light-sensitive emulsion layers, either alone or in a mixture thereof. The color photographic light-sensitive material as described in the item 1.