JPH0659368A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance graininess, low and high illuminance reprocity law failure characteristics, and sensitivity and to reduce fluctuation by forming at least one emulsion layer containing silver halide grains, at least one kind of specified compound, and at least one kind of DIR compound on a support. CONSTITUTION:The emulsion layer contains the compound represented by formula I in an amount of >=1X10<-7>mol per mol of silver halide and iridium in an amount of >=1X10<-10>mol and the emulsion layer and its adjacent layer contain the DIR compound in an amount of >=1X10<-3>mol. In formula I, Z is a nonmetallic atomic necessary to form an aromatic ring; R<1> is H, 1-5C alkyl; R<2> is 1-8C alkyl optionally substituted by halogen, hydroxy, carboxy, or sulfo; and X<-> is a counter anion, but it is not needed when N<+>-R<2> forms betaine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a halogen having little processing fluctuation, high sensitivity, and improved graininess and high illuminance / low illuminance reciprocity law failure. The present invention relates to a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials are desired to have high sensitivity and good graininess. Conventionally, development inhibitor releasing couplers (DIR couplers) have been used to improve graininess. In recent years, a large amount of DIR couplers have been used especially for improving graininess. For this reason, the graininess is improved in the medium illuminance region in the vicinity of the exposure time 1/100 "which is usually used, but on the other hand, the sensitivity reduction and the softening occur in the low illuminance region of the 1/10" to 10 "region. The undesirable phenomenon that the sensitivity decreases and the softening occurs even in the high illuminance region of 1/10000 ″ to 1/100 ″ that is commonly used in stroboscopic photography is also an undesirable phenomenon. In addition, the treatment liquid is contaminated by a large amount of DIR couplers, and the problem that the performance tends to fluctuate due to the treatment liquid frequently occurs.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color light-sensitive material which has excellent graininess, low illuminance / high illuminance reciprocity law characteristics, high sensitivity, and little processing fluctuation. Is.

[0004]

The above object is to provide an emulsion layer containing (1) silver halide grains, at least one compound represented by the following general formula (I), and at least one DIR compound. In the silver halide color photographic light-sensitive material having at least one layer support, the content of the compound represented by the general formula (I) contained in the emulsion layer is 1 to 1 mol of the silver halide in the emulsion layer. × 10 ^-7 mol or more, D contained in the emulsion layer and a layer adjacent to the emulsion layer
A silver halide color photographic light-sensitive material characterized by having an IR compound content of 5 × 10 ⁻³ mol or more, and the emulsion layer containing Ir of 1 × 10 ⁻¹⁰ mol or more, a general formula (I):

[0005]

[Chemical 2] (In the formula, Z is a group of non-metal atoms necessary for forming an aromatic ring, R ¹ is H, alkyl having 1 to 5 carbon atoms, R ² is a halogen atom, a hydroxyl group, a carboxyl group, or a sulfo group. An optionally substituted alkyl group having 1 to 8 carbon atoms, X ⁻ is a counter anion.

However, when forming betaine with N ⁺ -R ² , X ^- is unnecessary. (2) The silver halide according to the above (1), wherein the DIR compound is a DIR coupler having a development inhibitor or a development inhibitor precursor which loses the development inhibiting ability in an alkaline developer after being released from the coupling active position. Color photographic light-sensitive material, and (3) tabular silver halide grains having an aspect ratio of 3 or more account for 50% of the projected area of all silver halide grains in the emulsion layer.
This is achieved by the silver halide color photographic light-sensitive material described in (1) above.

The details of the present invention will be described below. (1) Silver Halide Emulsion Grain The silver halide grain used in the silver halide light-sensitive material of the present invention is not particularly limited in size, composition and morphology, but the following are preferably used. Regarding the composition, in AgBr _1-x I _x , 0 ≦ x ≦ 0.2 is preferable, and 0 ≦ x ≦ 0.14 is particularly preferable. Regarding the grain size, the diameter of the sphere equivalent to the volume weighted average value of the silver halide grains (diameter in terms of sphere) is preferably 0.05 μm to 1.8 μm, and particularly preferably 0.2 μm to 1.4 μm.
The morphology of the particles is preferably tabular from the viewpoint of improving color sensitization and sharpness. in this case,
The aspect ratio is preferably 3 or more and less than 8 and 4 or more and 7.5.
Less than is particularly preferred. Here, the aspect ratio is
It is a value obtained by dividing the diameter of a circle having an area equal to the area of the principal plane of a tabular grain by the thickness of the grain. Silver halide grains of various forms and structures can be prepared by methods well known in the art.

The silver halide emulsion in the present invention is chemically sensitized. For chemical sensitization, for example, H. H. Frieser ed., Di Grundlagel del Photography Shen Protsese Mitt
Die Grundlagen
der Photographischen Pro
sesse mit Silverhalogenid
en) (Academy Michel Ferrags Gesell Shackt,
1968) pp. 674-734 can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver (eg, thiosulfates, thioureas, mercapto compounds, rhodanins);
Reduction sensitization using a reducing substance (eg, stannous salt, amine salt, hydrazine derivative, formamidinesulfinic acid, silane compound); noble metal compound (eg, gold complex salt, Pt, Ir, Pd) Noble metal sensitization method using group VIII metal complex salts of the Periodic Table, selenium compounds (eg, selenoureas, selenoketones, selenides)
Alternatively, a selenium sensitization method or a tellurium sensitization method using a tellurium compound can be used. In the present invention, gold sulfur sensitization, gold sulfur selenium sensitization, and gold sulfur tellurium sensitization are preferably used.

The silver halide emulsion of the present invention may or may not be color-sensitized with a sensitizing dye, but is preferably color-sensitized. As the sensitizing dye, those having a main absorption wavelength in the range of 300 to 800 nm can be appropriately used according to the purpose and application of the light-sensitive material. The sensitizing dye may be added at any position in the silver halide emulsion manufacturing process and the photosensitive material coating liquid manufacturing process.
It is preferably added in the step of producing a silver halide emulsion, and particularly preferably after the desalting step of the silver halide emulsion, before chemical sensitization, or at the initial stage of chemical sensitization.

In the present invention, Ir may be added during the step of preparing a silver halide emulsion or during the step of preparing a coating solution. Doping into the silver halide grains is preferred.
Regarding the position of Ir doping, it may be doped once in any step of silver halide emulsion preparation, or may be doped several times. The preferred dope position is preferably after the nucleation of silver halide grains and before the end of chemical sensitization.
It is particularly preferable before the desalting step. The total amount of Ir to be doped is 1 per 1 mol of the total Ag amount of the silver halide emulsion.
It may be at least ¹⁰ × 10 ^-10 mol, but is preferably at least 1 × 10 ^-9 mol, particularly preferably at least 1 × 10 ^-8 mol. The silver halide emulsion of the present invention can be doped with Ir in any form. In the present invention, Ir is preferably doped into the silver halide grain as a tetravalent or trivalent cation in the preparation liquid of the silver halide emulsion, and is preferably doped into the silver halide grain as a tetravalent cation. Is particularly preferred. (2) Compound represented by the general formula (I) In the compound represented by the general formula (I), a preferable structure is represented by the general formula (II).

[0012]

[Chemical 3] (In the formula, R ² is CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H
_{9, C 5 H 11, (} CH 2) 3 SO 3 -, (CH 2) 4 S
O ₃ ⁻ and X ⁻ are Br ⁻ , I ⁻ , H ₃ C—C ₆ H.
₄ -SO ₃ ^- represents a. ) General formula (III)

[0013]

[Chemical 4] (In the formula, R ¹ is H, CH ₃ , and R ² is (C
H ₂ ) ₃ SO ₃ ⁻ and (CH ₂ ) ₄ SO ₃ ⁻ . )
The following FC-1 to FC-6 can be mentioned as particularly preferable structures.

[0014]

[Chemical 5] The compound represented by the general formula (I) may be added at any position in the silver halide emulsion manufacturing process and the coating liquid manufacturing process, but it is preferably added in the silver halide emulsion manufacturing process. Further, it is preferably added at the time of chemical sensitization in the production process of the silver halide emulsion, and particularly preferably at the end of the chemical sensitization. The addition amount may be 1 × 10 ⁻⁷ mol or more with respect to 1 mol of silver halide in the silver halide emulsion layer to be added, but 5 ×
10 ⁻⁶ to 1 × 10 ⁻³ mol is preferable, and 1 × 10 ^{−5 to} 5 ×
10 ⁻⁴ mol is particularly preferred. Further, a combination of the compound represented by the general formula (I) with a tetrazaindene compound or a mercapto compound which is commonly used in the art is also preferably used. When used in combination with these compounds, it is preferable to add the compound represented by the general formula (I) before the compound to be used in combination.

The examples of the tetrazaindene compound and the mercapto compound which can be preferably used in combination in the present invention are shown below.

[0016]

[Chemical 6] (3) DIR Compound In the present invention, the DIR compound is a compound which releases a development inhibitor by a coupling reaction with an oxidized product of an aromatic primary amine developer. As such a DIR compound, a DIR coupler is preferably used. DIR
The structure of the coupler is not particularly limited, and those well known in the art can be appropriately used.

The amount of DIR compound is determined by the formula (I) above.
Ratio of silver halide (amol) contained in the emulsion layer to the total amount (cmol) of the DIR compound contained in the silver halide emulsion layer containing the compound of (1) and the layer adjacent to the emulsion layer.
/ A) is 5 × 10 ⁻³ or more, preferably 8 × 10 ⁻³ or more, and particularly preferably 1.3 × 10 ⁻² or more.

The DIR coupler preferably used as the DIR compound in the present invention is represented by the following general formula (IV) and general formula (VI).

General Formula (IV) A- (TIME) _n -B In the formula, A is a coupler residue which leaves (TIME) _n -B by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Represents a timing group that binds to the coupling active position of A and releases B after leaving from A by the coupling reaction, and B represents the following general formula (Va), (Vb), (Vc), (Vd), (V
e), (Vf), (Vg), (Vh), (Vi), (V
j), (Vk), (Vl), (Vm), (Vn), (V
o) or (Vp), and n represents an integer of 0 or 1. However, when n is 0, B is directly bonded to A.

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9] In the formula, X ₁ represents a substituted or unsubstituted aliphatic group having 1 to 4 carbon atoms or a substituted phenyl group. X ₂ is a hydrogen atom,
Aliphatic group, halogen atom, hydroxyl group, alkoxy group, alkylthio group, alkoxycarbonyl group, acylamino group, carbamoyl group, sulfonyl group, sulfonamide group, sulfamoyl group, acyloxy group, ureido group, cyano group, nitro group, amino group Represents an alkoxycarbonylamino group, an aryloxycarbonyl group or an acyl group, X ₃ represents an oxygen atom, a sulfur atom or an imino group having 4 or less carbon atoms, and m represents an integer of 1 or 2. However, the total number of carbon atoms contained in m X ₂ is 8 or less, and when m is 2, the two X ₂ may be the same or different.

General formula (VI)

[0024]

[Chemical 10] In the formula, Y reacts with an oxidized product of a developing agent to obtain (L ₁ ) _v -Z-
(L ₂ ) represents a group that cleaves _w- DI, L ₁ represents a linking group that cleaves a bond with Y and then a bond with Z, and Z reacts with an oxidized product of a developing agent (L ₂ ) Represents a group capable of cleaving _w- DI, and L ₂ is D after the bond with Z is cleaved.
Represents a group that cleaves I, DI represents a development inhibitor,
v and w each represent an integer of 0 to 2, and when they represent 2, two L _{1 s} and two L _{2 s} each represent different or the same. (4) Hydrolyzable DIR Compound In the present invention, the hydrolyzable DIR compound is a development inhibitor or a fragment of a development-inhibiting precursor which loses its inhibitory property after being released from the coupling active position by the reaction of color development. Anything can be used as long as you have it.
In the present invention, a compound represented by the following general formula (VII) can be preferably used as the hydrolyzable compound.

General formula (VII)

[0026]

[Chemical 11] In the formula, m is 0, 1, n is 1, 2, C _p is a coupler, Z is the whole or main structure of the development inhibiting agent, and the coupling position of the coupler means directly when m = 0. , When m = 1, it is bonded via T, Y is bonded to Z via the linking group L, and a substituent that exerts the development inhibitory action of Z, and L is a chemical bond that is cleaved in the developing solution. A linking group containing n = 2
At this time, L and Y may be different or the same.

Preferred couplers represented by the general formula (VII) are represented by the following general formulas (VIII) to (XVI).

[0028]

[Chemical 12]

[0029]

[Chemical 13] In the general formulas (VIII) to (XVI), R ₁ is a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureido group, cyano group, nitro group, sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxyl A group, a sulfo group, a cycloalkyl group, an alkanesulfonyl group, an arylsulfonyl group or an acyl group, R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group, κ is 1 or 2,
When k is 2, a plurality of R _{1 s} may form a heterocycle, and X is contained in the Z part in the general formula (VII), and is a hydrogen atom, a halogen atom, an alkyl group, Represents an alkenyl group, alkaneamide group, alkenamide group, alkoxy group, sulfonamide group or aryl group, Y is an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group or a hetero group. It represents a ring group, and L is a linking group.

Examples of the linking group preferable as L are shown below together with the substitution position of Z and the substitution position of Y.

[0031]

[Chemical 14]

[0032]

[Chemical 15] However, d represents an integer of 0 to 10, preferably 0 to 5, W ₁ is, for example, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and 1 to carbon atoms.
10, preferably 1 to 5 alkoxy groups, 1 to 1 carbon atoms
0, preferably 1 to 5 alkoxycarbonyl group, aryloxycarbonyl group, 1 to 10 carbon atoms, preferably 1 to 5 alkanesulfonamide group, aryl group, carbamoyl group, 1 to 10 carbon atoms, Preferably 1-5 N-
Alkylcarbamoyl group, nitro group, cyano group, aryl
Selected from a sulfone amide group, a sulfamoyl group and an imide group, W ₂ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or an alkenyl group, and W ₃ represents a halogen atom, a nitro group or a carbon number. It represents an alkoxy group of 1 to 6.

The above-mentioned emulsions may be used alone in the light-sensitive emulsion layer, or may be mixed with two or more emulsions having different average grain sizes or two or more emulsions having different average silver iodide contents to obtain the same light-sensitivity. You may use in a layer. The use of a mixture of emulsions controls the gradation, controls the graininess from the low exposure area to the high exposure area, and depends on the color development (time and, for example, the developing solution of the color developing agent sodium sulfite salt). It is preferable from the viewpoint of control of internal composition dependence and pH dependence.

The light-sensitive material of the present invention may be provided with at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer 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. This photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side.
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.

The intermediate layer may be formed, for example, in JP-A-61-4.
No. 3748, No. 59-113438, No. 59-113
No. 440, No. 61-20037, No. 61-20038
A coupler as described in the specification, a DIR compound may be contained, and a color mixing inhibitor may be contained as is commonly used.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are composed of 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 structure of a sensitivity emulsion layer can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each silver halide emulsion layer. Further, for example, JP-A-57-112751, JP-A-57-12751
2-200350, 62-206541, 62
As described in JP-A-206543, 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, the low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (B
H) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH
/ RL, or BH / BL / GH / GL / RL / R
It can be installed in the order of H.

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, JP-A-56-25738 and JP-A-62-63.
As described in Japanese Patent No. 936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

As described in JP-B-49-15495, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a lower layer in the lower layer. An example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity than that of the middle layer is arranged and the photosensitivity is gradually decreased toward the support, and three layers having different sensitivities are arranged. 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, in the case of four or more layers, the arrangement can be changed as described above.

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

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

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferably silver iodide,
The content is 0.5 to 10 mol%.

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

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically 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 coated silver amount of the light-sensitive material of the present invention is 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 three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1989) 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, page 649, right column, 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention page 24 to 25 page 649 right column 868 to 870 page agents and stabilizers 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, to page 650, left column, ultraviolet absorbers 7. Stain page 25 right column page 650 left column page 872 Inhibitor to right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder page 26 page 651 left column 873 to page 874 11. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 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, immobilization 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 includes, for example, JP-A-1-106.
No. 052, it is preferable to add a compound which releases a fog, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention includes the international publication WO88.
No. 04794, Dyes or EP317,308A dispersed by the method described in JP-A-1-502912.
U.S. Pat. No. 4,420,555, JP-A-1-259.
It is preferable to incorporate the dye described in No. 358.

Various color couplers can be used in the present invention. Specific examples thereof are Research Disclosure No. 17643, VII-CG, and N
o. 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 EP 249,473A are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and examples thereof include US Pat. Nos. 4,310,619 and 4,35.
No. 1,897, European Patent No. 73,636, US Patent Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (198
June, 4), JP-A-60-33552, Research Disclosure No. 24230 (June 1984)
Mon), JP-A-60-43659, JP-A 61-72238.
No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Pat. No. 4,500,63.
No. 0, No. 4,540, 654, No. 4,556, 6
No. 30, those described in International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,052,212 and 4,146,396.
No. 4,228,233, No. 4,296,200
No. 2, No. 2,369,929, No. 2,801,17
No. 1, No. 2,772, 162, No. 2,895, 8
No. 26, No. 3,772,002, No. 3,758,
No. 308, No. 4,334, 011 and No. 4,32
7,173, West German Patent Publication No. 3,329,729,
European Patent Nos. 121,365A and 249,453A
U.S. Pat. Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
Those described in 690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
No. 64-554, No. 64-555, and No. 64-556.
The pyrazoloazole-based couplers described in U.S. Pat. No. 4,849,639 and the imidazole-based couplers described in U.S. Pat.

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

Examples of couplers in which the coloring 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 Research Disclosure N.
o. 17643, Item VII-G, ibid. 30710
5, section VII-G, U.S. Pat. No. 4,163,670,
Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,9
29, 4,138,258, British Patent 1,1.
Those described in No. 46,368 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, VII-F section and No. 307105, V
Patents described in the section II-F, JP-A-57-15194
No. 4, 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.

As couplers which imagewise release a nucleating agent or a development accelerator during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
The compounds described in JP-A-45687, which release a fogging agent, a development accelerator, and a silver halide solvent by a redox reaction with an oxidized product of a developing agent are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat.
Competitive couplers described in US Pat. No. 30,427, for example, US Pat. Nos. 4,283,472 and 4,338,393,
Multiequivalent couplers described in JP-A No. 4,310,618, such as JP-A-60-185950 and JP-A-62-242.
52, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 31
No. 3,308A, a coupler that releases a dye that recolors after release, for example, a ligand-releasing coupler described in US Pat. No. 4,555,477, and a leuco dye described in JP-A-63-75747. The couplers and the couplers emitting a fluorescent dye described in US Pat. No. 4,774,181 can be mentioned.

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

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

Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include:
Phthalates (for example, 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), esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri- 2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (for example,
2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (Eg, isostearyl alcohol, 2,4-di-t
ert-amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg, N, N) -Dibutyl-2
-Butoxy-5-tert-octylaniline) and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). The auxiliary solvent has, for example, a boiling point of about 30 ° C. or higher, preferably 50
An organic solvent having a temperature of not lower than 160 ° C and not higher than about 160 ° C can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

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, for example,
Phenethyl alcohol and JP-A-63-257747,
No. 62-272248, and JP-A-1-80941.
1,2-benzisothiazolin-3-one described in No.
It is possible to add various preservatives or fungicides such as n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. preferable.

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 which can be used in the present invention are described in, for example, RD. No. 17643, page 28,
Same No. 18716, page 647, right column to page 648, left column,
And the same No. 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, can be measured by using a type of Swellometer described (swelling meter) pp 124-129, T _1/2 is 30 ° C. with a color developing solution, and treated for 3 minutes 15 seconds 90% of the maximum swollen film thickness that reaches at time is the saturated film thickness,
It is defined as the time required to reach 1/2 of the saturated film thickness.

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

The photosensitive 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, pages 28-29, ibid. 1
8716, page 651, left column to right column, and the same No. 307
Development processing can be carried out by a usual method described on page 880-881.

The color developing solution used in the development processing of the light-sensitive material in 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 typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 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 sulfates, hydrochlorides or p- Toluene sulfonate may be mentioned. Among these, especially 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds are 2 depending on the purpose.
It is also possible to use together more than one species.

The color developer contains, for example, a pH buffering agent such as an alkali metal carbonate, borate or phosphate.
It is common to include development inhibitors or antifoggants such as chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvent such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic 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 their salts can be used.

When the reversing process is carried out, the black and white development is usually carried out before the color development. This black-and-white developer contains known black-and-white developing agents, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or amino acids such as N-methyl-p-aminophenol. Phenols can be used alone or in combination.

The pH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 L (liter) or less per 1 m 2 of the light-sensitive material, and 500 ml can be obtained by reducing the bromide ion concentration in the replenishing solution. It can also be: 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 expressed 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, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set within a range of 2 to 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent. 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, for example, polyvalent metal compounds such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents are iron (III) complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid,
Complex salts of aminopolycarboxylic acids such as glycol ether diamine tetraacetic acid, citric acid, tartaric acid, or malic acid can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment 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 iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators include, for example, U.S. Pat. No. 3,893,858 and West German Patent 1,290,81.
2, No. 2,059,988, JP-A-53-3273.
No. 6, No. 53-57831, No. 53-37418,
53-72623, 53-95630, 53
-95631, No. 53-104232, No. 53-1
No. 24424, No. 53-141623, No. 53-28
No. 426, Research Declosure No. 1712
No. 9 (July 1978), compounds having a mercapto group or a disulfide group; JP-A-50-1401.
Thiazolidine derivatives described in No. 29; JP-B-45-85
06, JP-A-52-20832, and JP-A-53-3273.
5, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-5
Iodide salts described in 8-16,235; West German Patent No. 96
6,410, 2,748,430, polyoxyethylene compounds; JP-B-45-8836, polyamine compounds; and others, JP-A-49-40,943.
No. 49-59,644, and 53-94,927.
No. 54, 35-727, 55-26, 506.
No. 58-163, 940; and bromide ions. Of these, compounds having a mercapto group or a disulfide group are preferred because of their large accelerating effect. In particular, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95,630 are disclosed. The compounds mentioned are preferred. Further, US Pat. No. 4,55
The compounds described in No. 2,834 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.

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

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, for example, a combined use of a thiosulfate solution and a thiocyanate, a thioether compound, or thiourea is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

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

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 concrete method of strengthening the stirring, a method of causing a jet stream of a processing solution to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and a rotating means described in JP-A-62-183461 are used. To improve the stirring effect, and further to move the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution to make the emulsion surface turbulent, thereby further improving the stirring effect, the entire processing solution. There is a method of increasing the circulation flow rate of. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. 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, as a result, increases 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 for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, 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 photographic light-sensitive material in the present invention is generally subjected to a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive 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 methods such as countercurrent and forward flow, and various other conditions Can be set in a wide range. Among these, the relationship between the number of washing tanks and the water amount in the multi-stage counterflow method is as follows.
tty of Motion Picture
Television Engineers, 64th
Volume 248 to 253 (May 1955 issue).

According to the multistage countercurrent method described in the above document,
Although the amount of washing water can be significantly reduced, bacteria increase due to an increase in the residence time of water in the tank, for example, a problem arises in that the produced suspended matter adheres to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. Also,
The isothiazolone compounds described in JP-A-57-8542, siabendazoles, chlorine-based germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (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 the 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 washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C and 20 seconds to 10 seconds.
Minutes, preferably at 25-40 ° C. for 30 seconds-5 minutes. 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 stabilization treatment, Japanese Patent Laid-Open No. 57-8543
All known methods described in Nos. 58-14834 and 60-220345 can be used.

Further, there is a case where a stabilizing treatment is further carried out after the water washing treatment. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. Can be mentioned. 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, indoaniline compounds described in U.S. Pat. No. 3,342,597, No. 3,342,599, Research Disclosure No. 14, 850 and the same No. Fifteen, fifteen
9, Schiff base type compounds described in No. 9, aldol compounds described in No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A No. 53-135628. it can.

The silver halide color light-sensitive material of the present invention comprises
If necessary, various 1-phenyl-3-pyrazolidones may be incorporated for the purpose of promoting color development. Typical compounds are JP-A-56-64339 and JP-A-57-144.
547 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 comprises
For example, U.S. Pat. No. 4,500,626, JP-A-60
-133449, 59-218443, 61-
It is also applicable to the photothermographic materials described in 238056 and European Patent 210 660A2.

[0098]

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 seed crystal emulsion α) JP-A-63-151618
US Pat. No. 4,797,354, West German Patent 3,70
Referring to No. 7,135-A1, the following double-structured silver iodobromide tabular silver halide seed crystal emulsion α was prepared.

Core: 33% of total seed crystal silver Shell: 67% of total seed silver thiourea dioxide 6.3 × 10 ^{−6 with} respect to total seed silver
After mol / molAg was present to form a shell, C ₂ H ₅ —SO ₂ S—Na was added at 2.5 × 10 ⁻⁴ mol / molAg with respect to the total silver of the seed crystal, and the mixture was aged for 4 minutes. (Preparation of EM-1) Seed crystal emulsion α (silver
(Contains 155 g in terms of gNO ₃ and 36 g of gelatin)
While stirring, the following (1-1a solution) and (1-1b solution)
Were added simultaneously over 5 minutes. (1-1a solution) while keeping the _{AgNO 3 7g H 2 O 200cc (} 1-1b solution) KI 5.5g H ₂ O 200cc then 8.5 pAg, following (1-2a solution)
And (1-2b solution) were added simultaneously over 30 minutes. 5 of the total projected area of (1-2a _{solution) AgNO 3 71g H 2 O 300cc} (1-2b solution) silver halide grains contained in _{KBr 50g H 2 O 300cc EM-} 1
The aspect ratio was 5.1 at 0% or more. The aspect ratio was measured by randomly extracting 600 or more particles by electron microscope observation by the replica method. In addition, Coulter Counter T manufactured by US Coulter Electronic Co.
The volume-weighted average sphere-equivalent diameter (average diameter of spheres having the same volume as the volume of silver halide grains) obtained by measurement using AII type was 0.48 μm. (Preparation of EM-1-A) At the end of the chemical sensitization of EM-1 (optimum gold sulfur sensitization), a mercapto compound (above MER-
1) was added at 1.8 × 10 ⁻⁴ mol / mol Ag. This emulsion is designated as EM-1-A. (Preparation of EM-1-AI) In the preparation of EM-1-A, 30 seconds before addition of (1-1a solution) and (1-1b solution), the following (1-3 solution) was added. (1-3 Solution) K ₂ IrCl ₆ 6.63 × 10 ⁻⁵ g H ₂ O 10 cc An emulsion prepared in the same manner as EM-1-A except for the above was EM-.
1-AI. (Preparation of EM-1-B) Replace MER-1 of EM-1-A with F
EM except for changing to C-1 (7 × 10 ⁻⁵ mol / mol Ag)
EM-1-B was made exactly as for -1-A. (Preparation of EM-1-BI) An emulsion prepared in the same manner as in EM-1-B except that (1-3 solution) was added in the same manner as in the preparation of EM-1-AI in the preparation of EM-1-B. EM-
1-BI. (Preparation of EM-1-C) In the preparation of EM-1-B,
After adding FC-1 (7 × 10 ⁻⁵ mol / mol Ag),
E except that MER-1 was added at 6 × 10 ⁻⁵ mol / mol Ag
EM-1-C was made in the same manner as M-1-B. (Preparation of EM-1-CI) An emulsion prepared in the same manner as in EM-1-C except that (1-3 solution) was added in the same manner as in the preparation of EM-1-AI in the preparation of EM-1-C. EM-
1-CI. (Example 1) In this example, the DI of the embodiment of the present invention
R coupler amount and R. M. S. The relationship between granularity and high / low illumination reciprocity law is shown.

Samples 101 to 11 which are multilayer color light-sensitive materials composed of layers having the compositions shown below and in Table 1 on an undercoated cellulose triacetate film support.
Created 6. These samples 101 to 116 were imagewise exposed with white light at a shutter speed of 10 ^{-4 "} to 10",
The color development processing shown in the following processing method-1 was performed. After the development process, the RM with a shutter speed of 1/100 "is used.
S. Is measured through an aperture with an opening diameter of 48 μm,
The relative value of the reciprocal is defined as a measure of granularity and is shown in Table 2. The optical density of the sample was measured through a filter having the optical characteristics shown in FIG. Table 2 shows the relative values of the values obtained by subtracting the fog of yellow density from the maximum value of yellow density. The coating amount (Composition of photosensitive layer) is specified otherwise not as long as the amount represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, for additives and gelatin g / m ² The amount expressed in units is shown, and for the sensitizing dye, it is shown as the number of moles per mole of silver halide in the same layer. The coating amount of DIR-Cp-1,2 in the 12th layer is shown in Table 1 in terms of the molar ratio to the coating silver amount of the silver iodobromide emulsion Bu in the layer.

UV; UV absorber, Solv; high boiling organic solvent, ExF; paint, ExS; sensitizing dye, ExC; cyan coupler; ExM; magenta coupler, ExY; yellow coupler, Cpd; additive first layer (halation Preventive layer) Black colloidal silver 0.15 Gelatin 2.33 ExM-2 0.11 UV-1 3.0x10 ^-2 UV-2 6.0x10 ^-2 UV-3 7.0x10 ^-2 Solv -1 0.16 Solv-2 0.10 ExF- 1 1.0 × 10 -2 ExF-2 4.0 × 10 -2 ExF-3 5.0 × 10 -3 Cpd-7 1.0 × 10 - ³ Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.2 mol%, uniform AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 35%, plate-like grain, aspect ratio Ratio 3.1) Silver coating amount 0.35 Silver iodobromide emulsion (Ag 6.0 mol%, core-shell ratio 1: 2, internal high AgI type, sphere equivalent diameter 0.45 μm, variation coefficient of sphere equivalent diameter 23%, plate-like particles, aspect ratio 2.0) coated silver amount 0.18 gelatin 0.77 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.4 × 10 ⁻⁴ ExS-5 2.3 × 10 ⁻⁴ ExS-7 4.1 × 10 ⁻⁶ ExC-1 9.0 × 10 ^-2 ExC-2 2.0 x 10 ^-2 ExC-3 4.0 x 10 ^-2 ExC-4 2.0 x 10 ^-2 ExC-5 8.0 x 10 ^-2 ExC-6 2.0 x 10 ^-2 ExC-9 1.0 x 10 ^-2 Third layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 5.9 mol%, core-shell ratio 1: 2, internal high AgI type, sphere equivalent) Diameter 0.67 μm, variation coefficient of spherical equivalent diameter 35%, plate-like particles, aspect ratio 2.3) Coating amount of silver 0.80 Gelatin 1.46 ExS-1 2.4 ^{10 -4 ExS-2 1.4 × 10} -4 ExS-5 2.4 × 10 -4 ExS-7 4.3 × 10 -6 ExC-1 0.19 ExC-2 1.0 × 10 -2 ExC -3 2.5x10 ^-2 ExC-4 1.6x10 ^-2 ExC-5 0.19 ExC-6 2.0x10 ^-2 ExC-7 3.0x10 ^-2 ExC-8 1. 0 × 10 ^-2 ExC-9 3.0 × 10 ^-2 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 8.9 mol%, core-shell ratio 3: 4: 2 multi-structured grains) , AgI content from the inside 24,0,6 mol%, sphere equivalent diameter 0.80 μm, variation coefficient of sphere equivalent diameter 42%, plate-like particles, aspect ratio 2.5) Coating silver amount 1.05 Gelatin 1.38 ^{ExS-1 2.0 × 10 -4 ExS} -2 1.1 × 10 -4 ExS-5 1.9 × 10 -4 ExS-7 1.4 × 10 -5 ExC-1 8.0 × 1 ^{-2 ExC-4 9.0 × 10 -2} ExC-6 2.0 × 10 -2 ExC-9 1.0 × 10 -2 Solv-1 0.20 Solv-2 0.53 5th layer (intermediate layer ) Gelatin 0.62 Cpd-1 0.13 Polyethyl acrylate latex 8.0 × 10 ^-2 Solv-1 8.0 × 10 ^-2 6th layer (low sensitivity green sensitive emulsion layer) Silver iodobromide emulsion (AgI 3.7 mol%, uniform AgI type, sphere equivalent diameter 0.45 μm, variation coefficient of sphere equivalent diameter 20%, plate-like particles, aspect ratio 4.5) Coating silver amount 0.13 Gelatin 0.31 ExS-3 1 0.0 × 10 ^-4 ExS-4 3.1 × 10 ^-4 ExS-5 6.4 × 10 ^-5 ExM-1 0.12 ExM-3 2.1 × 10 ^-2 Solv-1 0.09 Solv- 4 7.0 × 10 ^-3 seventh layer (medium-sensitivity green-sensitive emulsion layer) silver iodobromide emulsion (AgI 4.2 mol%, uniform gI type, sphere-corresponding diameter 0.69 .mu.m, variation coefficient of 25% equivalent spherical diameter, the plate-like particles, the aspect ratio 4.0) coating silver amount 0.31 Gelatin ^{0.54 ExS-3 2.7 × 10 -4} ExS ^{-4 8.2 × 10 -4 ExS-5} 1.7 × 10 -4 ExM-1 0.27 ExM-3 7.2 × 10 -2 ExY-1 5.4 × 10 -2 Solv-1 0. 23 Solv-4 1.8 × 10 ^-2 Eighth Layer (High Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 8.5 mol%, silver amount ratio 3: 4: 2 multi-structured grains, AgI content) From inside the amount: 24, 0, 3 mol%, sphere equivalent diameter 0.69 μm, variation coefficient of sphere equivalent diameter 51%, multiple twin plate particles, aspect ratio 2.7) coated silver amount 0.49 gelatin 0.61 ExS-4 4.3 × 10 ^-4 ExS-5 8.6 × 10 ^-5 ExS-8 2.8 × 10 ^-5 ExM-2 1.0 × 10 ^{-2 ExM-5 1.0 × 10 -2} ExM-6 3.0 × 10 -2 ExY-1 1.5 × 10 -2 ExC-1 0.4 × 10 -2 ExC-4 2.5 × 10 ^-3 ExC-6 0.5x10 ^-2 Solv-1 0.12 Cpd-8 1.0x10 ^-2 9th layer (intermediate layer) Gelatin 0.56 Cpd-1 4.0x10 ^-2 Poly Ethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2 UV-4 3.0 × 10 ^-2 UV-5 4.0 × 10 ^-2 10th layer (multilayer effect on red-sensitive layer) Donor layer) Silver iodobromide emulsion (AgI 7.5 mol%, internal high AgI type grain having a core-shell ratio of 1: 2, sphere equivalent diameter 0.70 μm, variation coefficient of sphere equivalent diameter 35%, multiple twin plate-like) Grain, aspect ratio 2.0) Coating silver amount 0.67 Silver iodobromide emulsion (AgI 10.0 mol%, core-shell ratio 1: 3, high internal AgI) Particles, spherical equivalent diameter 0.45 [mu] m, a variation coefficient of 17% equivalent spherical diameter, regular crystal grains, the coating silver amount 0.20 Gelatin ^{0.87 ExS-3 6.7 × 10 -4} ExM-4 0.16 Solv- 1 0.30 Solv-6 3.0 × 10 ^-2 11th layer (yellow filter layer) Yellow colloidal silver 9.0 × 10 ^-2 gelatin 0.84 Cpd-2 0.13 Solv-1 0.13 Cpd- 1 5.0 × 10 ⁻² Cpd-7 2.0 × 10 ⁻³ H-1 0.25 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion-Bu Coated silver amount 0.80 (7 .42 × 10 ⁻³ mol / m ² ) Gelatin 2.18 ExS-6 9.0 × 10 ⁻⁴ ExC-1 0.05 DIR-Cp-1 x DIR-Cp-2 y ExY-4 1.09 Solv -1 0.54 13th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 14 %, Internal high AgI type particles having a core-shell ratio of 1: 2, equivalent spherical diameter of 1.4 μm, variation coefficient of equivalent spherical diameter of 65%, twin) Coating silver amount 0.40 Gelatin 0.59 ExS-6 2.6 × 10 ^-4 ExY-4 0.20 ExC-1 1.0 × 10 ^-2 Solv-1 9.0 × 10 ^-2 14th layer (first protective layer) Fine grain silver iodobromide emulsion (AgI 2.0 Mol%, uniform AgI type, equivalent spherical diameter 0.07 μm) Coating amount of silver 0.12 Gelatin 0.63 UV-4 0.11 UV-5 0.18 Solv-5 2.0 × 10 ^-2 Cpd-50 .10 Polyethyl acrylate latex 9.0 × 10 ^-2 Fifteenth layer (second protective layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, equivalent spherical diameter 0.07 μm) Coating silver amount 0.36 gelatin 0.85 B-1 (diameter 2.0μm) 8.0 × 10 ^-2 B 2 The (diameter ^{2.0μm) 8.0 × 10 -2 B-} 3 2.0 × 10 -2 W-4 2.0 × 10 -2 H-1 0.18 thus prepared samples, above the other 1,2-benzisothiazolin-3-one (average of 2 for gelatin)
00 ppm), n-butyl-p-hydroxybenzoate (about 1000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. Furthermore, B-4, B-5, F-1, F-2, F-3, F-4, F
-5, F-6, F-7, F-8, F-9, F-10, F
-11, F-12 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained.

In addition to the above components, each layer contains a surfactant W.
-1, W-2, and W-3 were added as a coating aid or an emulsifying dispersant.

[0103]

[Chemical 16]

[0104]

[Chemical 17]

[0105]

[Chemical 18]

[0106]

[Chemical 19]

[0107]

[Chemical 20]

[0108]

[Chemical 21]

[0109]

[Chemical formula 22]

[0110]

[Chemical formula 23]

[0111]

[Chemical formula 24]

[0112]

[Chemical 25]

[0113]

[Chemical formula 26]

[0114]

[Chemical 27]

[0115]

[Chemical 28]

[0116]

[Chemical 29]

[0117]

[Chemical 30]

[0118]

[Chemical 31]

[0119]

[Chemical 32]

[0120]

[Chemical 33]

[0121]

[Chemical 34]

[0122]

[Chemical 35] Processing method-1 Process processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ℃ 45ml 10 liters Bleach 1 minute 00 seconds 38 ℃ 20ml 4 liters Bleach fixing 3 minutes 15 seconds 38 ℃ 30ml 8 liters Washing (1 ) 40 seconds 35 ℃ From (2) to (1) 4 liters countercurrent piping system Washing with water (2) 1 minute 00 seconds 35 ℃ 30ml 4 liters Stabilized 40 seconds 38 ℃ 20ml 4 liters Dry 1 minute 15 seconds 55 ℃ The amount of replenishment is per 35 mm width and 1 m length. Next, the composition of the treatment liquid will be described. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriamine pentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1 3.0 3.2-Diphosphonic acid Sodium sulfite 4.0 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- (N-ethyl-N-β-hydro 4.5 5.5 5.5 Xyethylamino) -2-methyl aniline sulphate Add water 1.0 liter 1.0 liter pH 10.05 10.10 (bleaching liquor) mother liquor, replenisher common (unit g) ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0 disodium ethylenediaminetetraacetate 10.0 ammonium bromide 100.0 ammonium nitrate 10.0 bleaching accelerator {(CH _{3) 2} N- _{H 2 CH 2 -S} 2 ·} 2HCl 0.005 mole Ammonia water (27%) 15.0 ml Water to make 1.0 l pH 6.3 (Bleach-fixing solution) Mother liquor, replenisher common (in g) ethylenediamine Ferric ammonium tetraacetate dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia water (27%) 6.0 ml Add water 1 0.0 liter pH 7.2 (Washing liquid) Mother liquor and replenisher common tap water is H type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR). -400) is passed through a mixed bed type column to adjust the concentration of calcium and magnesium ions to 3 mg / liter or less. Then, 0.15 g / l of sodium sulfate with 20 mg / l of sodium isocyanurate dichloride was added.
The pH of this liquid was in the range of 6.5-7.5. (Stabilizer) Mother liquor, replenisher common (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water Add 1.0 liter

[0123]

[Table 1]

[0124]

[Table 2] From Table 2, the samples according to the embodiments of the present invention show that R. M. S. Even if the granularity is improved, the yellow density [(maximum value)-
It can be seen that the change in the relative value of (fog value)] is small and the reciprocity law characteristic is excellent. (Example 2) In this example, the relation between the addition amount of Ir and the addition amount of the compound of the general formula (I) and the reciprocity law property is shown in the range where the number of DIR couplers according to the embodiment of the present invention is relatively large. In the above-mentioned preparation of EM-1-BI, the addition amount of Ir and / or the addition amount of the compound of the general formula (I) was changed as shown in Table 3 below to prepare emulsions (Samples 201 to 211).
Was prepared. Table 4 shows the results of examining the reciprocity law characteristics of these samples by exposing and treating them in the same manner as in Example 1. It can be seen from Table 4 that the reciprocity law property is improved when the added amounts of Ir and the compound of the general formula (I) are within the ranges described in the present invention.

[0125]

[Table 3]

[0126]

[Table 4] (Example 3) This example shows the dependence of the present invention on the amount of the compound of the general formula (I) and the dependence on the aspect ratio of silver halide emulsion grains. EM- except that the addition amount of FC-1 and the seed crystal emulsion at the end of the chemical sensitization of EM-1-BI shown in Example 1 were changed.
EM-3-a to i were produced in exactly the same manner as 1-BI. Further, in the preparation of the seed crystal emulsion α of Example 1, various tabular seed crystal emulsions β having the same size but different aspect ratios were prepared by appropriately changing the pAg during and immediately after the nucleation. By using these seed crystal emulsions β, silver halide emulsions EM-3-a to i having the same size as EM-1-BI but having different aspect ratios were prepared.
Further, using these silver halide emulsions, Samples 301 to 309 were prepared in the same manner as in the method described in Example 1.
Table 5 shows the configuration of the twelfth layer of these samples. Table 6 shows the results of examining the high illuminance / low illuminance reciprocity law characteristics and the relative sensitivity of these samples. Here, the photographic sensitivity is a relative value of an optical density on a fog of yellow density of 1.5 when a white imagewise exposure is applied at a shutter speed of 10 ^-2 "and the same color development processing as in Example 1 is performed. Sensitivity, where relative sensitivity is the optical density on fog 1.
Using the exposure amount E (CMS) corresponding to the position of 5 and the exposure amount Es of the reference sample, (relative sensitivity) = (Es / E) × 100. From Table 6 the compound FC in the general formula (I)
It can be seen that -1 has a preferable use area as described above. It is also found that there is a preferable region as described above with respect to the aspect ratio of silver halide grains.

[0127]

[Table 5]

[0128]

[Table 6] (Example 4) In this example, the effect of the hydrolyzable DIR compound on the process variation will be described. Samples 401 to 406 were manufactured by changing DIR-Cp-1 and DIR in Sample 205 of Example 2 as shown in Table 7. This sample was continuously processed according to the following processing method-2. The treatment was carried out until the replenisher solution in the stabilizing tank was three times as large as that in the stabilizing tank. In this example, only one type of DIR-Cp was added in the twelfth layer. Sample 40 was prepared in the same manner as in Example 3.
1 to 406 image-like white exposure with shutter speed 1
0 gradation fluctuation when given by ^-2 "(maximum absolute gamma difference | delta
γ |) is shown in Table 8. According to Table 8, hydrolysis type DI
It can be seen that by using the R coupler, gradation variation (maximum absolute gamma difference | Δγ |) due to the running treatment liquid is small and a more stable image can be obtained.

Processing method-2 (Processing step) Process processing time Processing temperature Complementary amount Color development 1 minute 40 seconds 40 ° C 50 ml Bleach 40 seconds 38 ° C 5 ml Fixed 1 minute 20 seconds 38 ° C 30 ml Stable ( 1) 20 seconds 38 ℃ -Stable (2) 20 seconds 38 ℃ -Stable (3) 20 seconds 38 ℃ 40ml Dry 1 minute 15 seconds 55 ℃ * Replenishment amount is 35mm width per 1m length * Stable (3) Countercurrent system from (1) to (1) The composition of the treatment liquid is shown below. (Color developer) Tank solution Replenisher (g / l) (g / l) Hydroxyethyliminodiacetic acid 3.0 3.0 Sodium 1,2-dihydroxybenzene-3,5-disulfonate 1.0 1.0 Sodium sulfite 3.0 4.0 Potassium carbonate 30.0 35.0 Potassium bromide 1.0 0.4 Hydroxylamine sulfate 2.5 3.5 4- [N-ethyl-N-β-hydroxyethylamino] -2-methianiline sulfate 6.5 7.5 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.02 0.03 5-Nitroindazole 0.02 0.03 pH (using potassium hydroxide and water) 10.50 10.70 (bleaching solution) Tank solution Replenishing solution (g / l) (g / l) 1,3-diaminopropanetetraacetic acid ferric acid Ammonium dihydrate 60.0 75.0 Ferric ammonium diamine tetraacetate ammonium dihydrate 120.0 140.0 Ammonium bromide 160.0 190.0 Ammonium nitrate 30.0 35.0 pH (using acetic acid and ammonia water) 5.0 4.5 (Fixer) Tank solution Replenisher (g / l) (g / l) Ammonium thiosulfate aqueous solution (700 g / l) 400.0 ml 420.0 ml Sodium sulfite 12.0 15.0 Ethylenediaminetetraacetic acid disodium salt 1.0 1.0 pH (using acetic acid and ammonia water) 7.1 7.5 (Stabilizing solution) Tank solution Replenishing solution (g / l) (g / l) 5-chloro-2-methyl-4-isothiazoline -3-one 0.006 0.006 2-methyl-4-isothiazolin-3-one 0.003 0.003 formalin (37%) 1.0 ml 1.0 ml polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.05 0.05 pH 4.0-8.0 4.0-8.0

[0130]

[Table 7]

[0131]

[Table 8]

[0132]

As described above, according to the present invention, it is possible to obtain a silver halide color photographic light-sensitive material which is excellent in graininess, low illuminance / high illuminance reciprocity law characteristics, has high sensitivity, and has little processing variation. .

[Brief description of drawings]

FIG. 1 is a graph showing the optical characteristics of a filter used for measuring the optical density of a sample in an example of the present invention.

Claims (3)

[Claims] 1. A silver halide grain, at least one compound represented by the following general formula (I), and at least 1.
In a silver halide color photographic light-sensitive material having at least one emulsion layer containing one kind of DIR compound on a support, 1 mol of the silver halide in the emulsion layer represents the formula (I) contained in the emulsion layer. The content of the compound represented by 1) is 1 × 10 ⁻⁷ mol or more, the content of the DIR compound contained in the emulsion layer and a layer adjacent to the emulsion layer is 5 × 10 ⁻³ mol or more, and the emulsion is A silver halide color photographic light-sensitive material characterized in that the layer contains 1 × 10 ^-10 mol or more of Ir. General formula (I) In the formula, Z is a non-metal atom group necessary for forming an aromatic ring, R ¹ is H, alkyl having 1 to 5 carbon atoms, and R ² is a halogen atom, a hydroxyl group, a carboxyl group, or a sulfo group. An optionally substituted alkyl group having 1 to 8 carbon atoms, X ⁻ is a counter anion. However, when forming betaine with N ⁺ -R ² , X ^- is unnecessary. 2. The D-containing compound has a development inhibitor or a development inhibitor precursor which loses the development inhibiting ability in an alkaline developer after being released from the coupling active position.
The silver halide color photographic light-sensitive material according to claim 1, which is an IR coupler. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein tabular silver halide grains having an aspect ratio of 3 or more occupy 50% or more of the projected area of all silver halide grains in the emulsion layer.