JPH05173305A - Silver halide color negative photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce color turbidity and to enhance color reproduction performance, sensitivity, and storage stability of a raw stock by forming an interlayer between a red-sensitive layer and another color-sensitive layer containing a specified compound and enhancing sensitivity to a specified value. CONSTITUTION:The red-sensitive silver halide emulsion layers are formed as follows; the lowest sensitive layer nearest to a support, the middle sensitive layer next to this layer, and the highest sensitive layer farthest from the support. At least one of the interlayer between the red-sensitive layers and the other color sensitive layer contains the compound represented by formula I in which COUP1 is a main coupler component; BALL is a ballasting group combining with the coupling site of COUP1 and releasable by reaction of the coupler with the oxidation product of a color developing agent and allowing the compound to resist to diffusion; and SOL is a solubilizing group. The sensitivity of the photosensitive material is set to >=ISO-320. The interlayer outside the highest red sensitive emulsion layer farthest from the support and the interlayer inside the lowest red sensitive layer nearest to a support also contain this compound of formula I.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color negative photographic light-sensitive material having no color turbidity, excellent color reproducibility and improved raw storability of the light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION A silver halide color photographic light-sensitive material is generally composed of a plurality of silver halide emulsion layers having different color sensitivities. The plurality of silver halide emulsion layers include a blue light-sensitive layer and a green light-sensitive layer. It is generally provided with a photosensitive layer and a red photosensitive layer.

After exposing such a color photographic light-sensitive material,
Upon color development, the color developing agent forms an oxide in each color-sensitive layer, and the oxidation product reacts with the coupler in each color-sensitive layer to form a color. However, in each color-sensitive layer, when the silver halide is contained in a large excess relative to the coupler, the developing agent that has penetrated into each color-sensitive layer forms a large excess of oxide in the coupler, and Excessive oxidation product remains.

This excess oxidation product may further diffuse into the adjacent layer and react with the coupler in the other color-sensitive layer to deteriorate the color reproducibility. This results in a further decrease in image quality as the photographic constituent layers tend to become thinner.

Therefore, conventionally, the diffusibility of the oxidation product itself is prevented, or a scavenger for the oxidation product is added to the layer, for example, a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative or a sulfonamidephenol type compound. U.S. Pat.No. 2,360,290,
2,336,327, 2,403,721, 2,418,613, 2,6
75,314, 2,701,197, 2,704,713, 2,728,65
No. 9, No. 2,732,300, No. 2,735,765, No. 3,700,453,
JP-A-50-92988, 50-92989, 50-93928, 50
-110337, 50-156438, 52-146235, 55-9594
No. 8, No. 59-5247, and Japanese Patent Publication No. 50-23813 are disclosed.

However, these conventional techniques are apt to cause desensitization to each color-sensitive layer and do not provide the expected effect in terms of color reproducibility, and further development of new techniques is strongly desired. It was rare.

[0007]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a silver halide color negative photographic light-sensitive material having less color turbidity and excellent color reproducibility. The second object of the present invention is to
It is an object of the present invention to provide a silver halide color negative photographic light-sensitive material having high sensitivity and improved raw storability of the light-sensitive material. Other objects will be apparent from the following specification.

[0008]

The above objects of the present invention have been achieved by the following.

That is, (1) in a silver halide color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer on a support, the red-sensitive layer is a low-sensitivity silver halide from the side closer to the support. An emulsion layer, a medium-speed silver halide emulsion layer, and a high-speed silver halide emulsion layer, which are applied in this order in a three-layer structure, and at least one intermediate layer between the red-sensitive layer and another color-sensitive layer. A silver halide color negative photographic light-sensitive material containing at least one of compounds represented by the following general formula (C), wherein the sensitivity of the silver halide color photographic light-sensitive material is ISO-320 or more. Material, and (2) the intermediate layer outside the high-sensitivity red-sensitive silver halide emulsion layer on the side far from the support and the inner intermediate layer on the low-sensitivity red-sensitive silver halide emulsion layer near the support. Both of the intermediate layers contain at least the compound represented by the following general formula (C). Is accomplished by a silver halide color negative photographic light-sensitive material of (1) claim, wherein the containing one.

[0010]

[Chemical 2]

[0011] In the formula, COUP ₁ represents a coupler mother nucleus having a coupling site (asterisk), BALL is bonded to the coupling site of COUP _1, COUP upon reaction with an oxidation product of COUP ₁ with a color developing agent Represents a group capable of leaving from ₁ , which makes the compound resistant to diffusion. SOL represents a solubilizing group.

The present invention will be described in detail below.

The intermediate layer containing the compound of formula (C) in the present invention is preferably provided adjacent to the red-sensitive silver halide emulsion layer. In a preferred embodiment of the present invention, an intermediate layer outside the high-sensitivity red-sensitive silver halide emulsion layer far from the support and a low-sensitivity red-sensitive silver halide emulsion layer near the support. Both of the inner intermediate layers contain at least one of the compounds represented by the following general formula (C).

Specifically, the red-sensitive silver halide emulsion of the present invention is sandwiched with the intermediate layer of the present invention.
Therefore, the intermediate layer according to the present invention should not be adjacent to any color-sensitive layer other than the red-sensitive silver halide emulsion layer of the present invention. Preferably, one or more other intermediate layers are further provided between the intermediate layer of the present invention and the color-sensitive layers other than the red-sensitive silver halide emulsion layer.

The compounds represented by the general formula (C) according to the present invention include the following types.

(1) A coupler in which a dye formed by coupling with an oxidant of a color developing agent is eluted into a processing solution,
(2) Coupling with the oxidant of the color developing agent,
(3) A coupler which remains in a leuco form, and a dye produced by coupling with an oxidized product of a color developing agent does not have a noticeable visible absorption and gives a substantially colorless product.

Therefore, the general formula (C) is further subdivided and represented by the following general formulas (C-2) to (C-13), which are a group including compounds particularly preferred in the present invention.

[0018] In the formula, COUP ₁ represents a coupler mother nucleus having a coupling site (asterisk *), BALL is bonded to the coupling site of COUP _1, reaction with an oxidation product of the COUP ₁ with a color developing agent Is a group capable of splitting off from COUP _1, and is a stable group having a size and shape that makes the compound of the general formula (C) resistant to diffusion.

[0019] The SOL is a solubilizing group, attached to the non-coupling position of COUP _1, COUP ₁ and when color development coupling product generated by the coupling with an oxidation product of a color developing agent or after In the above, it is a group that imparts mobility to flow out of the photosensitive material to the outside of the system.

As the coupler mother nucleus represented by COUP ₁ ,
To form a colored or colorless reaction product by a coupling reaction with an oxidant of a color developing agent,
Mention may be made of any coupler nucleus known or used in the art.

BALL is a stable group having a large molecular shape that makes the compound of the general formula (C) diffusion resistant, and is limited as long as the compound of the general formula (C) imparts the diffusion resistance. Non-limiting examples of useful groups represented by BALL include alkyl groups having 8 to 32 carbon atoms, aryl groups and heterocyclic groups.

These groups include those which are substituted, but as a substituent, the compounds of the general formula (C) increase the diffusion resistance, change the reactivity of the compounds of the general formula (C), or It is a group that increases the diffusivity of BALL after a ring reaction and withdrawal. Further, it is also preferable that BALL is bound to the coupling site of COUP ₁ via a linking group.

The solubilizing group represented by SOL is a group that imparts mobility to the coupling product generated by the coupling reaction so that the coupling product can flow out of the photosensitive material, such as an ionizable hydroxyl group, a carboxyl group, and a sulfo group. Groups and aminosulfonyl groups and their ionizable salts and ester groups, ether groups and the like.

It is also preferred that one or more of these groups are attached to the uncoupling site of COUP ₁ , or of an appropriate size, for example an alkyl group having 1 to 10 carbon atoms, 6 to 12 carbon atoms. Those in which a solubilizing group in which the aryl group having a carbon atom has one or more of the above-mentioned ionizable groups are bound to the uncoupling site of COUP ₁ are also advantageously used.

It is also preferable that it is bound to the non-coupling site of COUP ₁ via a linking group.

[0026] Particularly preferred solubilizing groups are bonded directly to a non-coupling site of COUP ₁ directly bonded to a carboxyl group into a non-coupling position, a sulfo group or ionizable salts thereof, or COUP _1,, or amino group, or An alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms containing one or more carboxyl groups, sulfo groups or ionizable salts thereof, which are bonded via a carbonyl group. Is mentioned.

Further, the DP 'scavengers capable of forming the yellow, magenta and cyan dyes preferably used can be represented by the following general formulas (C-2) to (C-7).

[0028]

[Chemical 3]

[Yellow dye-forming compound] In the formula, Rc ₁ is an aryl group or an alkyl group (particularly a tertiary alkyl group), Rc ₂ is the above-mentioned stable group (BALL), and Rc ₃ is the above-mentioned solubilizing group. Rc ₄ is a hydrogen atom or a halogen atom, an alkyl group or an alkoxy group, and n +
m ≦ 5 (however, when n ≠ 0 and m ≠ 0, and when n and m are 2 or more, they may be the same or different.) [Magenta dye-forming compound]

[0030]

[Chemical 4]

[0031]

[Chemical 5]

General formulas (C-3), (C-4) and (C-
In the formula 5), Rc ₂ has the same meaning as Rc ₂ in formula (C-2), Rc ₅ represents a solubilizing group (SOL), and Rc ₆ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Alternatively, it represents an amino group and p ≦ 5 (provided that p ≠ 0 and when p is 2 or more, they may be the same or different). One of Rc ₇ and Rc ₈ represents the solubilizing group (SOL) described above, and the other represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an amino group. Rc ₉
And Rc ₁₀ are Rc ₇ and Rc in the general formula (C-4).
Synonymous with c ₈ .

In the formulas (C-6) and (C-7),
Rc ₂ has the same meaning as Rc _{2 in} formula (C-2), and Rc ₁₁
And at least one of Rc ₁₂ is a solubilizing group (SO
L) and the rest represent a hydrogen atom or a halogen atom, an alkyl group, an alkoxy group or an alkylamido group,
q ≦ 3 (however, q ≠ 0), and Rc ₁₃ represents the solubilizing group (SOL) described above.

Unless otherwise indicated above, alkyl, alkoxy, and alkylamido groups each contain from 1 to 8 carbon atoms, aryl groups contain from 6 to 10 carbon atoms, and Amino groups include primary, secondary and tertiary amino groups. These substituents and stable groups (BALL) also include those further substituted with groups such as halogen atom, hydroxyl, carboxyl, amino, amido, carbamoyl, sulfamoyl, sulfonamide, alkyl, alkoxy and aryl groups.

Examples of the compound belonging to (2) above include compounds represented by the following general formula (C-8).

[0036]

[Chemical 6]

In the formula, COUP ₂ has the same meaning as COUP ₁ in the general formula (C-1), Rc ₁₄ is bonded to the coupling site of COUP ₂ , the coupler of the general formula (C-8) and the color developing agent. Represents a group that cannot be removed by the reaction with the oxidant of.

As the coupler nucleus represented by COUP ₂ ,
The nucleus nucleus described in the general formula (C-1) can be mentioned. Examples of the group represented by Rc ₁₄ include an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group and a cyano group.

The compound represented by the general formula (C-8) is COU
It is preferable that the non-coupling site of the coupler mother nucleus represented by P ₂ is diffusion resistant with a linking group, an aryl group and a heterocyclic group.

Examples of the compound belonging to the above (3) include compounds represented by the following general formula (C-9).

[0041]

[Chemical 7]

In the formula, COUP ₃ represents a coupler nucleus which gives a substantially colorless product by a coupling reaction with an oxidant of a color developing agent, and Rc ₁₅ is bonded to a coupling site of COUP ₃ . Represents a group capable of leaving COUP ₃ by a coupling reaction with an oxidized product of a color developing agent.

Among the compounds represented by the general formula (C-9), more preferred are the general formulas (C-10) to (C-13).
Can be expressed as

[0044]

[Chemical 8]

In the formula, Rc ₁₅ has the same meaning as Rc ₁₅ in formula (C-9), and Rc ₁₆ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acyloxy group or a heterocyclic group, X is an oxygen atom or = NR
represents c ₁₇ . Rc ₁₇ represents an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or a sulfonyl group. Z
Represents a group of non-metal atoms necessary for forming a carbocycle (for example, indanone, cyclopentanone, cyclohexanone, etc.) or a heterocycle (for example, piperidone, pyrrolidone, hydrocarbostyril, etc.) on pages 5 to 7.

[0046]

[Chemical 9]

[0047] In the formula, Rc _15, Rc ₁₆ and X have the same meanings as Rc _15, Rc ₁₆ and X in the general formula (C-10), Rc ₁₆ represents an alkyl group, an aryl group, a heterocyclic group, a cyano group, It represents a hydroxyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylamino group, a dialkylamino group or an anilino group.

[0048]

[Chemical 10]

In the formula, Rc ₁₅ is R in the general formula (C-9).
synonymous with c ₁₅ , R c ₁₉ and R c ₂₀ may be the same or different, and an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, a formyl group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, It represents an ammonium group or the following.

[0050]

[Chemical 11]

A represents a group of non-metal atoms necessary for forming a 5- to 7-membered heterocyclic ring (eg, phthalimide, triazole, tetrazole, etc.) with a nitrogen atom.

[0052]

[Chemical 12]

In the formula, Rc ₁₅ has the same meaning as Rc _{15 in} formula (C-9), Rc ₂₁ represents an alkyl group, an aryl group, an anilino group, an alkylamino group or an alkoxy group, and B represents an oxygen atom or sulfur. Represents an atom or imino group.

The compounds represented by formulas (C-2) to (C-13) are disclosed in JP-A-59-113440, JP-A-59-171955 and JP-A-52-82423.
No., British Patents 914,145, 1,284,649, U.S. Patent 2,74
2,832, 3,227,550, 3,928,041, 3,958,993
No. 3, No. 3,961,959, No. 4,046,574, No. 4,052,231,
It can be synthesized by the method described in No. 4,419,886.

Next, typical examples of the compounds according to the present invention will be given, but the present invention is not limited thereto.

[0056]

[Chemical 13]

[0057]

[Chemical 14]

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

The addition amount of the compound represented by the general formula (C) according to the present invention is preferably in the range of 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per 1 m ² , and further, 1 × 10 ⁻⁵ to 1 ×. It is preferably used in the range of 10 ⁻³ mol.

The method of adding the compound represented by the general formula (C) according to the present invention is to emulsify and disperse in a high boiling point solvent and add it to the intermediate layer as an emulsified dispersion. As a method of addition, a known method, for example, the method described in US Pat. No. 2,322,027 is used, and the solid dispersion method described in European Patent 353,629 can also be applied.

The sensitivity of the light-sensitive material in the present invention is determined according to the test method described below. (JIS K7614-19
According to 81. (1) Test method The test is conducted in a room at a temperature of 20 ± 5 ° C and a relative humidity of 60 ° C ± 10%. The photosensitive material to be tested is left in this state for 1 hour or more before use.

(2) Exposure The relative spectral energy distribution of the reference light on the exposure surface is as shown in Table 1.

[0066]

[Table 1]

[0067]

[Table 2]

The illuminance change on the exposed surface is carried out by using an optical wedge, and in any part of the optical wedge used, the variation of the spectral transmission density is within 10% in the wavelength region of 360 to 700 nm, within 10% in the region of 400 nm or more, and in the region of 400 nm or more. Use within 5%.

The exposure time is 1/100 second.

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

The development treatment is completed within 30 minutes to 6 hours after the exposure.

The development process is performed as follows.

1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ℃ 2. Bleach 6 minutes 30 seconds 38.0 ± 3.0 ℃ 3. Washing with water 3 minutes 15 seconds 24-41 ° C 4. Settling 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Washing with water 3 minutes 15 seconds 24-41 ° C 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Drying 50 ° C or less The composition of the processing liquid used in each step is shown below.

(Color developer) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxyamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter (pH = 10.1) (bleaching solution) Ethylenediaminetetraacetate iron (III) ) Ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water is added to adjust the pH to 1 and the pH is adjusted to 6.0 with aqueous ammonia.

(Fixer) Ammonium thiosulfate 175.0 g anhydrous sodium sulfite 8.5 g sodium metasulfite 2.3 g Water was added to make 1 liter, and pH was adjusted to 6.0 with acetic acid.

(Stabilizing Solution) Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

(4) Concentration measurement The concentration is represented by Log ₁₀ (Φ ₀ / Φ). Φ ₀ is an illumination light flux for density measurement, and Φ is a transmitted light flux of the measured portion. The geometric condition for density measurement is that the illumination light flux is a parallel light flux in the normal direction, and the standard is to use the total light flux that is transmitted as a transmitted light flux and diffused in a half space, and standard when other measurement methods are used. Correct with density strips. Also, during the measurement, the emulsion film surface shall face the light receiving device side. Density is measured with blue, green, and red status M densities, and its spectral characteristics are set to the values shown in the table below as the overall characteristics of the light source, optical system, optical filter, and light receiving device used for the densitometer. ..

[0078]

[Table 3]

[0079]

[Table 4]

(5) Determination of ISO Sensitivity The ISO sensitivity is determined by the following procedure using the results of processing and concentration measurement under the conditions shown in (1) to (4).

For each minimum density of blue, green and red,
The exposure dose corresponding to a high density of 0.15 is expressed in lux · second and is designated as HB, HG, and HR, respectively.

The larger value (lower sensitivity) of HB and HR is designated as HS.

The ISO sensitivity S is calculated according to the following formula.

[0084]

[Equation 1]

In the present invention, the silver halide emulsion is Research Disclosure 308119 (hereinafter abbreviated as RD308119).
It is possible to use those described in.

Next, the description place is shown.

[Item] [Page of RD308119] Production Method 993 I-A and 994 E Item Iodine composition 〃 IA Item Crystal habit Normal crystal, Twin 〃 〃 Epitaxial 〃 〃 Halogen composition Uniform and non-uniform 993 I-B item Halogen conversion 994 I-C item 〃 Substitution 〃 Metal-containing item 994 I-D item Monodispersed 995 I-F item Solvent addition 〃 〃 Latent image forming position Surface, internal 995 I-G item Sensitive material negative Item 995 I-H Item mixed and used 〃 I-J Item Desalting 〃 Item II-A In the present invention, the silver halide emulsion is used after physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are Research Disclosure No.17643, No.18716 and No.308119 (respectively,
(Hereinafter abbreviated as RD17643, RD18716 and RD308119). The following is the description location.

Various couplers can be used in the present invention, specific examples of which are described in Research Disclosure above.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC to G item Magenta coupler 1001 VII-D item VIIC to G item Colored coupler 1002 VII-G item VIIG item BAR coupler 1002 VII- Item F Other useful residues Release coupler 1001 VII-F Item Alkali-soluble coupler 1001 VII-E The additives used in the present invention can be added by the dispersion method described in RD308119XIV.

In the present invention, RD17643, page 28, R
The supports described in D18716, pages 647-8 and RD308119, XVII can be used.

The light-sensitive material of the present invention includes VI of RD308119 described above.
Auxiliary layers such as the filter layer and the intermediate layer described in the item I-K can be provided.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, E, F to K Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known compounds usable in the present invention Photographic Additives are also described in Research Disclosure above.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII C Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricants 1006 XII 27 650 Activators / coating aids 1005 XI 26 to 27 650 Matte agents 1007 XVI Developers (contained in the photosensitive material) 1011 XXB Item The present invention is a color negative film or slide for general or movie use. It can be applied to various color light-sensitive materials represented by color reversal films, color papers, color positive films, and color reversal papers for televisions or televisions.

The light-sensitive material of the present invention is the above-mentioned RD17643 28-29.
Development can be carried out by a conventional method described on page RD18716, page 647 and RD308119, XVII.

[0095]

EXAMPLES Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

In all the following examples, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver. Further, the sensitizing dye is shown in mol / silver 1 mol.

Example 1 A multilayer color photographic light-sensitive material sample 101 was prepared by sequentially forming each layer having the following composition from the support side on a triacetyl cellulose film support.

Sample 101 First layer: Antihalation layer Black colloidal silver 0.16 UV absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer High boiling point solvent (Oil-1) 0.17 Gelatin 1.27 3rd layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content) Ratio 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-5 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-4 Sensitizing dye (SD -4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.70 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling point solvent (Oil-1) 0.53 Gelatin 1.30 4th layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 mol%) 0.62 Silver iodobromide emulsion (average grain size 0.38 μm m, silver iodide content 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.2 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.6 × 10 ^{− 5} Sensitizing dye (SD-4) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High boiling solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-4 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling solvent (Oil -1) 0.14 gelatin 0.91 6th layer: intermediate layer high boiling point solvent (Oil-2) 0.11 gelatin 0.80 7th layer: intermediate layer high boiling point solvent (Oil-2) 0.11 gelatin 0.80 8th layer: low sensitivity green sensitive layer Silver bromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.61 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD-4 ) 7.4 × 10 ^-5 Sensitizing dye (SD-5) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil- 2) 0.75 Gelatin 1.95 9th layer: Medium-sensitive green sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.87 Sensitizing dye (SD-6) 2.4 × 10 ^-4 increase Sensitizing dye (SD-7) 2.4 × 10 ^-4 Magenta coupler (M-1) 0.058 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D- 3) 0.002 High boiling point solvent (Oil-2) 0.50 Gelatin 1.00 Layer 10: High sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol) %) 1.27 Sensitizing dye (SD-6) 1.4 × 10 ^-4 Sensitizing dye (SD-7) 1.4 × 10 ^-4 Magenta coupler (M-2) 0.084 Magenta coupler (M-3) 0.064 Colored magenta coupler (CM) -1) 0.012 High boiling point solvent (Oil-1) 0.27 High boiling point solvent (Oil-2) 0.12 Gelatin 1.0 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 High boiling point solvent (Oil) -2) 0.19 Gelatin 1.10 Formalin scavenger (HS-1) 0.20 12th layer: Intermediate layer Gelatin 0.60 Formalin scavenger (HS-1) 0.20 13th layer: Low sensitivity blue sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm) , Silver iodide content 8.0 mol%) 0.22 silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.03 sensitizing dye (SD-8) 4.9 × 10 ^-4 yellow coupler (Y -1) 0.75 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 14th layer: Medium-sensitive blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.30 Sensitizing dye (SD-8) 1.6 × 10 ^-4 Sensitizing dye ( SD-9) 7.2 × 10 ^-5 Yellow coupler (Y-1) 0.10 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 Fifteenth layer: First protective layer Silver iodobromide emulsion ( Average grain size 1.00 μm, silver iodide content 8.0 mol%) 0.85 Sensitizing dye (SD-8) 7.3 × 10 ^-5 Sensitizing dye (SD-9) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.80 16th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1 mol%) 0.40 Ultraviolet absorber (UV-1) 0.065 Ultraviolet absorber (UV-2) 0.10 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 17th layer Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, a coating aid Su-1 , Dispersion aid Su-2, viscosity modifier, hardener H-1, H-2, stabilizer ST-1, antifoggant AF-1, weight average molecular weight 1
Two AF-2 of 0,000 and 1,100,000 and a preservative DI-
1 of 9.4 mg / m ² was added.

The structural formulas of the various compounds used are shown below.

[0100]

[Chemical 19]

[0101]

[Chemical 20]

[0102]

[Chemical 21]

[0103]

[Chemical formula 22]

[0104]

[Chemical formula 23]

[0105]

[Chemical formula 24]

[0106]

[Chemical 25]

[0107]

[Chemical formula 26]

[0108]

[Chemical 27]

Then, the compound represented by the general formula (C) according to the present invention was added to each of the intermediate layers of the second layer and the sixth layer as shown in Table 5 below, and sample Nos. 101 to 109 were added. It was created.

[0110]

[Table 5]

The AS-1 (2,5-di) used as a comparison was used.
(-t-octylhydroquinone) was dissolved in the same amount of dioctylphthalate and ethyl acetate, then a gelatin solution containing sodium dodecylbenzenesulfonate was added, and the dispersion emulsified and dispersed by a homogenizer was applied as an intermediate layer.

Further, the compound represented by the general formula (C) according to the present invention was prepared and emulsified and dispersed in the same manner as in AS-1 to obtain an intermediate layer.

One part of each sample thus prepared was refrigerated and stored as a fresh sample, and another part was stored at a temperature of 40 ° C.
The sample was left in an atmosphere of 80% relative humidity for 7 days to obtain a raw storage test sample due to forced deterioration. These two samples were subjected to wedge exposure by a usual method and then subjected to the following development processing.

1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ℃ 2. Bleach 6 minutes 30 seconds 38.0 ± 3.0 ℃ 3. Washing with water 3 minutes 15 seconds 24-41 ° C 4. Settling 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Washing with water 3 minutes 15 seconds 24-41 ° C 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Drying 50 ° C or less The composition of the processing liquid used in each step is shown below.

(Color developer) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter. (PH = 10.0) (Bleaching solution) Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to make 1 liter, pH with ammonia water Adjust to 6.0.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 l, and pH is adjusted to 6.0 with acetic acid.

(Stabilizer) Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

Regarding the red-sensitive part of the obtained sample,
The red sensitivities of the forced deterioration samples when the red sensitivities of the No. 101 fresh samples were set to 100 are shown as relative sensitivities.

Further, the fog was represented by (ΔFog) as the fog increase value of the forced deterioration sample with respect to the fresh sample.

The obtained results are shown in Table 6.

[0121]

[Table 6]

From Table 6 above, the following can be seen.

(1) Sample No. in which the intermediate layer was provided only with gelatin.
In contrast to 101, the comparative samples 102, 104, and 106 to which AS-1 which is a scavenger of a conventional oxidation product was added were all slightly improved in the fog increase due to the forced deterioration with respect to the sample 101. The relative sensitivities are all decreased.

(2) On the other hand, Sample No. 1 containing the compound according to the present invention added to the intermediate layer. It can be seen that all of 103, 105, 107, 108, and 109 maintain the same sensitivity as Comparative Sample No. 101, with the fog increase due to forced deterioration being remarkably improved and the sensitivity being not lowered.

From the results of sample Nos. 103, 105 and 109,
The compound of the general formula (C) according to the present invention is used only in the second layer or in the sixth layer.
Use of both the second layer and the sixth layer can suppress an increase in fog due to forced deterioration and can obtain an increase in sensitivity, and thus can achieve the desired effect of the present invention, rather than using only a single layer. I understood.

Example 2 The color reproducibility was measured using the sample prepared in Example 1.
The measurement was evaluated by the degree to which the green density when the sample was subjected to red color development exposure and color development processing to give a red density of 1.0 was lower than that of the sample No. 1. In this case, variation coefficient (ΔDG)
It is shown that the larger the value is on the negative side, the better the color reproducibility.

Also, the sensitivity of sample No. 101 during red separation exposure was
The relative sensitivities of the respective 100 were calculated. The results obtained are shown in Table 7.

[0128]

[Table 7]

From Table 7 above, the following can be seen.

(1) 10 of the comparative sample using AS-1 which is a scavenger of a conventional oxidation product with respect to sample No. 101
As is clear from the results of Nos. 2, 104, and 106, although the color reproducibility is improved, the relative sensitivity is rather lowered.

(2) On the other hand, Sample No. 1 having the compound according to the present invention added to the intermediate layer. All of 103, 105, 107, 108 and 109 have significantly improved color reproducibility without lowering relative sensitivity with respect to comparative sample No. 101. In addition, sample No. 103,
From the results of 105 and 109, the compound of the general formula (C) according to the present invention was added to the second layer or the sixth layer rather than the second layer only.
It can be seen that a greater effect is obtained when added to both the layer and the sixth layer.

Example 3 Using the samples Nos. 101 to 109 prepared in Example 2, the ISO sensitivity was measured by the method described above. The results obtained are shown in Table 8.

[0133]

[Table 8]

From the above table, it can be seen that the samples No. 102, 104 and 106 using the conventional scavenger have higher ISO sensitivity than the sample No. 101 not using the scavenger. Also, from sample No. 103, 105, 109, the second layer, the sixth
Higher sensitivity can be obtained by using the compound according to the present invention in both layers.

[0135]

According to the present invention, a silver halide color negative photographic light-sensitive material having improved color reproducibility without lowering sensitivity can be obtained. Further, according to the present invention, it is possible to provide a silver halide color photographic light-sensitive material which is less likely to cause fog over time and has good storage stability.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer on a support, wherein the red-sensitive layer is a low-sensitivity silver halide emulsion layer from the side closer to the support, A three-layer constitution in which a medium-speed silver halide emulsion layer and a high-speed silver halide emulsion layer are coated in this order, and in at least one intermediate layer between the red-sensitive layer and another color-sensitive layer, A silver halide color negative photographic light-sensitive material containing at least one compound represented by the following general formula (C), wherein the sensitivity of the silver halide color photographic light-sensitive material is ISO-320 or more. .. 2. An intermediate layer on the outer side of the high-sensitivity red-sensitive silver halide emulsion layer farther from the support and an inner layer on the inner side of the lower-sensitive red-sensitive silver halide emulsion layer closer to the support. A silver halide color negative photographic light-sensitive material according to claim 1, wherein at least one of the compounds represented by the following general formula (C) is contained in both layers. Wherein, COUP ₁ represents a coupler mother nucleus having a coupling site (asterisk), BALL is bonded to the coupling site of COUP _1, COUP ₁ upon reaction with an oxidation product of COUP ₁ with a color developing agent
Represents a group capable of leaving the compound to be diffusion resistant.
SOL represents a solubilizing group.