JP2002162709A - Silver halide color photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photosensitive material which is high in sensitivity, excellent in color reproducibility, and moreover, improved in color reproducibility under a fluorescent light. SOLUTION: The silver halide color photosensitive material is constituted so that it has a photosensitive layer comprised of at least one red-light sensitive layer, one green-light sensitive layer, one blue-light sensitive layer, and one non-photosensitive layer respectively on one side of a supporting body, the blue-light sensitive layer contains at least one kind of a spectral sensitizing dye represented by general formula (SI) and a spectral sensitizing dye represented by general formula (SII) respectively, and the spectral sensitivity distribution of the blue-light sensitive layer satisfies the following relations. λS (80)>=55 nm and λS (50)<=90 nm, where λS (80) is the width of the spectral sensitivity distribution in 80% of the maximum sensitivity o the spectral sensitivity distribution, and λS (50) is the width of the spectral sensitivity distribution in 50% of the maximum sensitivity of the spectral sensitivity distribution.

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 (hereinafter, also referred to as "color light-sensitive material" or simply as "light-sensitive material"). The present invention relates to a silver halide color photographic material.

[0002]

2. Description of the Related Art Color light-sensitive materials are said to be mature products with a high degree of perfection. On the other hand, the required performance is wide-ranging, such as high sensitivity, high image quality, and little fluctuation in performance due to storage conditions. In the future, it is necessary to take into account rapid processing aptitude which has advanced development progress, etc., and the required level has been increasing more and more in recent years.

In addition, with the recent technological advances in digital cameras, in order to maintain the superiority of photographic light-sensitive materials, it is necessary to achieve both higher sensitivity, higher image quality, and faithful color reproduction.

Techniques for increasing the sensitivity of silver halide emulsions, that is, sensitization techniques, relate to a method for producing a silver halide emulsion, chemical sensitization of a silver halide emulsion, spectral sensitization of a silver halide emulsion, Various methods are known, such as those based on the design method of silver halide emulsions and those related to the development process of silver halide emulsions. It is essential for recording.

[0005] Spectral sensitization involves adsorbing certain cyanine dyes or merocyanine dyes onto a silver halide crystal and transmitting light energy having a wavelength absorbed by the dye to a photosensitive silver halide crystal as a carrier. It is performed by In the case of a blue-sensitive layer, it is general to sensitize using a spectral sensitizing dye in a wavelength region of 400 to 500 nm. Control of the spectral sensitivity is very important from the viewpoint of efficient spectral sensitization, color reproducibility, and suitability for different light sources. Until now, many techniques have been disclosed as preferred spectral sensitivity distributions of the blue-sensitive layer.

For example, Japanese Patent Application Laid-Open No. 10-268488 discloses that
It is described that the spectral sensitivity of the blue-sensitive layer is broadened toward the short wave side and the long wave side to increase the sensitivity.
From the viewpoint of color reproducibility, Japanese Patent Application Laid-Open No. 5-249626 describes that by suppressing the sensitivity in the long-wave portion of the blue-sensitive layer, the color reproducibility of greenish colors such as blue-green and yellow-green is improved. Have been. Further, JP-A-8-44009 and JP-A-8-54513 describe that the suitability for a fluorescent lamp is improved by relatively increasing the sensitivity (430 to 440 nm) of the short-wave portion of the blue-sensitive layer. .

However, these techniques have not been satisfactory from the viewpoint of achieving both high sensitivity and color reproducibility.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has as its object to provide a halogenated compound which has high sensitivity, excellent color reproducibility, and improved color reproducibility under a fluorescent lamp. An object of the present invention is to provide a silver color photographic light-sensitive material.

[0009]

It is an object of the present invention to provide a photographic light-sensitive material comprising, on one side on a support, at least one red-sensitive layer, one green-sensitive layer, one blue-sensitive layer and one light-insensitive layer. In a silver halide color photographic light-sensitive material having a light-sensitive layer, the blue-sensitive layer has a spectral sensitizing dye represented by the general formula (SI) and a spectral sensitizing dye represented by the general formula (SII). This is achieved by a silver halide color photographic light-sensitive material containing at least one kind of the dye "Chemical formula 2" and having the spectral sensitivity distribution of the blue-sensitive layer satisfying the following relationship.

ΛS (80) ≧ 55 nm λS (50) ≦ 90 nm Here, λS (80) is the maximum sensitivity of the spectral sensitivity distribution of 80.
% Represents the width of the spectral sensitivity distribution, and λS (50) represents the width of the spectral sensitivity distribution at 50% of the maximum sensitivity.

A silver halide color photographic light-sensitive material in which the spectral sensitivity distribution of the blue-sensitive layer satisfies the following relationship also achieves the object of the present invention.

ΛS (80) ≧ 55 nm S (400 nm) ≦ 60% Smax S (480 nm) ≦ 50% Smax where λS (80) is the maximum sensitivity of the spectral sensitivity distribution of 80.
% Represents the width of the spectral sensitivity distribution, Smax represents the maximum sensitivity, and S (400 nm) and S (480 nm) represent the sensitivity at 400 nm and 480 nm, respectively.

It is a preferred embodiment that the spectral sensitivity distribution of the blue-sensitive layer satisfies the following relationship.

430 nm ≦ λSmax ≦ 455 nm Here, λSmax represents the maximum sensitivity wavelength of the spectral sensitivity distribution.

It is also a preferred embodiment that the blue-sensitive layer contains silver halide grains having an aspect ratio of 8 or more.

Hereinafter, the present invention will be described in more detail. First, the spectral sensitizing dyes represented by the general formulas (SI) and (SII) will be described.

Y ₁ is a sulfur atom, a selenium atom or —N
(R ₃ ) —, and Y ₂ represents an oxygen atom. Y ₃ and Y ₄ each represent a sulfur atom or a selenium atom. Z ₁ , Z ₂ , Z ₃
And Z ₄ each represent an atom group necessary to form an optionally substituted benzene ring or naphthalene ring.
R ₁ , R ₂ , R ₄ and R ₅ each represent an aliphatic group, and R ₃ represents a lower alkyl group. X ₁ and X ₂ each represent a charge-balancing counter ion, and n1 and n2 each represent an integer for adjusting the charge of the entire molecule.

Examples of the group which can be substituted on the benzene ring or naphthalene ring formed by Z _{1 to} Z ₄ include lower alkyl groups (methyl, ethyl, propyl, i-propyl, t-pentyl,
Methylthioethyl, methoxyethyl, etc.), halogen atoms (fluorine, chlorine, bromine atom, etc.), vinyl group, styryl group,
Aryl group (phenyl, p-tolyl, p-bromophenyl, etc.), trifluoromethyl group, alkoxy group (methoxy, ethoxy, i-propyl, etc.), aryloxy group (phenoxy, p-tolyloxy, etc.), alkylthio group (methylthio , Ethylthio, benzylthio, etc.), arylthio groups (phenylthio, p-bromophenylthio, p
-Methoxyphenylthio, etc.), carbonyloxy group (acetyloxy, propanoyloxy, benzoyloxy, etc.), amino group (amino, dimethylamino, anilino, etc.), heterocyclic group (pyridyl, pyrrolyl, furyl, thienyl, imidazolyl, thiazolyl) , Pyrimidinyl, etc.), acyl group (acetyl, benzoyl, etc.), cyano group, carbamoyl group (carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, etc.), sulfamoyl group (sulfamoyl, N-phenylsulfamoyl, morpholinosulfonyl) ), An acylamino group (acetylamino, benzoylamino, o-hydroxybenzoylamino, etc.), a sulfonylamino group (methanesulfonylamino, benzenesulfonylamino, etc.), an alkoxycarbonyl group (methoxycal Cycloalkenyl, ethoxycarbonyl, trifluoromethyl ethoxycarbonyl), a hydroxyl group,
It can be arbitrarily selected from a carboxyl group, a sulfonyl group (methanesulfonyl, ethanesulfonyl, benzenesulfonyl, etc.), a trifluoromethylsulfinyl group and the like, and can be substituted at any position.

As the aliphatic group represented by R ₁ , R ₂ , R ₄ and R ₅ , for example, a branched or straight-chain alkyl group having 1 to 10 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, i-yl) -Pentyl, 2-ethylhexyl, octyl, decyl, etc.), an alkenyl group having 3 to 10 carbon atoms (2-propenyl, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1-methyl-3-butenyl) , 4-
Hexenyl) and aralkyl groups having 7 to 10 carbon atoms (benzyl, phenethyl and the like).

The above-mentioned groups further include a lower alkyl group, a halogen atom, a vinyl group, an aryl group, a trifluoromethyl group, an alkoxy group, an aryloxy group, a cyano group, a sulfonyl group, an alkoxycarbonyl group (ethoxycarbonyl group, butoxycarbonyl group). Etc.), amino group, aryl group, heterocyclic group, acyl group, ureido group (ureido, 3-
Methylureide, 3-phenylureide, etc.), thioureido group (thioureide, 3-methylthioureide, etc.),
Alkylthio group, arylthio group, heterocyclic thio group (2-
A group such as thienylthio, 3-thienylthio), a carbonyloxy group, an acylamino group, a thioamide group (such as thioacetamido or thiobenzoylamino), or a sulfo group;
Carboxyl group, phosphono group, sulfato group, hydroxyl group, mercapto group, sulfino group, carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.), sulfamoyl group (sulfamoyl, N, N-3-oxa) Pentamethyleneaminosulfonyl, etc.), sulfonamide group (methanesulfonamide, butanesulfonamide, etc.), sulfonylaminocarbonyl group (methanesulfonylaminocarbonyl, ethanesulfonylaminocarbonyl, etc.), acylaminosulfonyl group (acetamidosulfonyl, methoxyacetamidosulfonyl, etc.) ), Acylaminocarbonyl groups (acetamidocarbonyl, methoxyacetamidocarbonyl, etc.), sulfinylaminocarbonyl groups (methanesulfinylaminoca Boniru, ethanesulfinyl aminocarbonyl, etc.), may be substituted with a hydrophilic group such as a sulfoamino group.

Specific examples of the aliphatic group substituted with these hydrophilic groups include carboxymethyl, carboxyethyl, carboxybutyl, carboxypentyl, 3-sulfatobutyl, 3-sulfopropyl, 2-hydroxy-
3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 3-sulfopentyl, 3-sulfinobutyl,
3-phosphonopropyl, hydroxyethyl, N-methanesulfonylcarbamoylmethyl, N-acetylaminosulfonylmethyl, sulfoaminopropyl, 2-carboxy-2-propenyl, o-sulfobenzyl, p-sulfophenethyl, p-carboxybenzyl, etc. Each group of is mentioned.

(X ₁ ) _n1 , (X ₂ ) _n2 are included in the formula to indicate the presence or absence of a cation or an anion when necessary to neutralize the ionic charge of the dye. I have. Therefore, n1 and n2 can take an appropriate value of 0 or more as needed. Specific examples of typical cations include protons, organic ammonium ions (each ion such as triethylammonium, triethanolammonium, and pyridinium), and inorganic cations (each cation such as lithium, sodium, potassium, calcium, and magnesium). Specific examples of the acid anion include, for example, a halogen ion (each ion such as chlorine, bromine and iodine),
Acid ions (p-toluenesulfonic acid, perchloric acid, boron tetrafluoride, sulfuric acid, methylsulfuric acid, ethylsulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.) and the like.

Specific examples of the spectral sensitizing dyes represented by formulas (SI) and (SII) (hereinafter also referred to as blue-sensitive sensitizing dyes of the present invention) are shown below. It is not limited to these.

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The sensitizing dyes represented by the general formulas (SI) and (SII) are known compounds, for example, US Pat. Nos. 3,149,105 and 2,238,231 and British Patent 742. No. 112, or "The Cyanine Soybeans and Related Compound" by FM Harma (Interscience Publishers, N.M.
Y. , 1964), p. 55 et seq., Those without descriptions can be easily synthesized by a similar method.

The addition amount of the sensitizing dye of the present invention is preferably from 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, more preferably from 5 × 10 ^{−5 to} 5 × 10 per 1 mol of silver halide. ^-3 mol. When the dyes represented by the general formula (SI) and the general formula (SII) are used in combination, the molar ratio of the (SI) dye to the (SII) dye ranges from 1:50 to 50: 1. Is preferably, more preferably 1:20 to 20: 1, and particularly preferably 1:10 to 10: 1.

When adding the (SI) dye and the (SII) dye, the (SI) dye and the (SII) dye may be added simultaneously or separately to the silver halide emulsion.
Further, two or more (SI) dyes or two or more (SII) dyes may be used in combination.

As a method for adding the (SI) dye and the (SII) dye, a generally well-known method can be used. For example, a suitable solvent (methanol, ethanol, propanol, fluorinated alcohol, 1-methoxyethanol, water or an acid or alkali aqueous solution having a suitable pH value)
And dissolving in a volatile organic solvent, as described in US Pat. No. 3,469,987, and dispersing this solution in a hydrophilic colloid. Addition method to emulsion, JP-B-46-24185
Dissolving a water-insoluble dye, as described in
Alternatively, there is a method of dispersing in a water-soluble solvent and adding this dispersion to an emulsion.

In the present invention, the (SI) dye, (SI
I) It is preferable to add the dye in a solid state to the silver halide emulsion. In order to add the (SI) dye and the (SII) dye in a solid state to the silver halide emulsion, they can be added in the form of granules, in the form of powder, dispersed in an appropriate liquid, There is a method of adding as a dispersion.

In the present invention, (SI) dye, (SI)
I) A method is preferred in which the dye is dispersed in water in a state substantially free of an organic solvent, and is added to the emulsion as a dispersion.
In order to disperse the sensitizing dye in water substantially without an organic solvent, various dispersion methods are effectively used.
Specifically, a high-speed stirrer, a ball mill, a sand mill, a colloid mill, an attritor, an ultrasonic disperser, or the like is used. Among them, a high-speed stirrer is preferable.

The organic solvent is a solvent containing carbon atoms and liquid at room temperature. Conventionally, water-miscible organic solvents such as alcohols, ketones, nitriles, and alkoxy alcohols have been used as solvents especially for sensitizing dyes. Specifically, methanol, ethanol, propyl alcohol, i
-Propyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, acetone,
Acetonitrile, 2-methoxyethanol, 2-ethoxyethanol and the like can be mentioned. The present invention does not substantially contain these organic solvents.

The term "substantially free of an organic solvent" means that the above-mentioned organic solvent is 10% or less by mass, preferably 5% by mass with respect to water.
% Or less, particularly preferably 3% or less.

As a high-speed stirring type disperser, for example, FIG.
As shown in FIG. 1A, there is a tank comprising a tank 1, a dissolver 2, a vertical shaft 3, and a liquid 4 to be dispersed. FIG. 1 (b)
The impeller 5 and the wings 6 and 7 that constitute the dissolver 2
Is shown.

The high-speed stirring type disperser may have a dissolver having a plurality of impellers mounted on a vertical axis or a multi-axis dissolver having a plurality of vertical axes.
In addition to the dissolver alone, a high-speed stirring type disperser having an anchor blade is more preferable. As a specific working example, after water is put into a temperature-adjustable tank, a certain amount of the sensitizing dye powder is put, and the mixture is stirred for a certain period of time under a temperature control with a high-speed stirrer, crushed, Spread.

The pH and the temperature at the time of mechanically dispersing the sensitizing dye are not particularly limited. However, at low temperatures, the dispersion does not reach the desired particle size even after long-time dispersion, and re-aggregation or decomposition occurs at high temperatures. As a result, there is a problem that desired photographic performance cannot be obtained, and a problem that the viscosity of the solution system is lowered when the temperature is increased, so that the efficiency of pulverizing and dispersing solids is greatly reduced. Therefore, the dispersion temperature is preferably 15 to 50 ° C. Further, the stirring rotation speed at the time of dispersion requires a long time to obtain a desired particle size at a low rotation speed, and at too high a rotation speed, bubbles are involved and the dispersion efficiency is reduced. Dispersing is preferred.

The term "dispersion" as used in the present invention means a suspension of a sensitizing dye. Preferably, the dispersion in which the mass ratio of the sensitizing dye in the suspension is 0.2 to 5.0% is used. Can be

The dispersion of the sensitizing dye prepared according to the present invention may be added directly to the silver halide emulsion or may be appropriately diluted before addition. Is used. When dispersing the sensitizing dye in water, a surfactant can also be used. The surfactant referred to here is
There are anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

The (SI) dye and the (SII) dye may be dispersed simultaneously in water or separately.

The timing of adding the (SI) dye and the (SII) dye may be any time during the period from the formation of silver halide grains to immediately before coating, but after the completion of the formation of silver halide grains, chemical addition is performed. It is preferably added during the period until the feeling is finished. Particularly preferred is the case where it is added during the period from the completion of silver halide grain formation to before the addition of the chemical sensitizer.

The spectral sensitivity distribution of the blue-sensitive layer referred to in the present invention is defined as the reciprocal of the amount of exposure that gives a color photosensitive material spectral exposure at intervals of several nm from 400 to 700 nm and gives a constant density at each wavelength. Sensitivity, which is a function of wavelength.

In order to make the spectral sensitivity distribution of the blue-sensitive layer of the color light-sensitive material of the present invention, the above-mentioned (SI) dye and (SII) dye are controlled and other optional means are used in combination. I can do it. For example, adjusting a target spectrum by appropriately using an ultraviolet absorber is also an embodiment of the present invention. Further, the spectrum may be adjusted by optimizing the halogen composition and distribution of any silver halide grains.

In order to further exert the effect of the present invention, the maximum sensitivity wavelength λ (G) Smax of the spectral sensitivity distribution of the green-sensitive layer.
And the maximum sensitivity wavelength λ (R) Smax of the red-sensitive layer preferably has the following relationship.

530 nm ≦ λ (G) Smax ≦ 570 nm 595 nm ≦ λ (R) Smax ≦ 635 nm In the present invention, 50% or more of the total projected area of the silver halide used is tabular grains having an aspect ratio of 8 or more. Is preferred. More preferable is 50% of the total projected area.
The above are tabular grains having an aspect ratio of 10 or more, and particularly preferably, 50% or more of the total projected area has an aspect ratio of 15 or more.
These are the above tabular grains. The upper limit of the aspect ratio is about 50.

In the present invention, the aspect ratio (AR ratio) refers to the ratio of the grain size to the thickness of silver halide grains.
In the case of tabular silver halide grains, the diameter of the silver halide grains is a diameter obtained by converting a projected image viewed from a direction perpendicular to the main plane into a circular image having the same area, In the case of silver halide grains having a shape other than tabular silver halide grains, the diameter is obtained by converting a projected image of the silver halide grains into a circular image having the same area.

To determine the aspect ratio, first, the diameter and thickness of the silver halide grains are determined by the following method. A latex ball having a known particle diameter serving as an internal standard and a sample coated so that the main plane was oriented parallel to the support were prepared on a support, and shadow was applied from a certain direction by a carbon vapor deposition method. Thereafter, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area diameter and thickness of each silver halide grain are determined using an image processing device or the like. In this case, the thickness of the silver halide grains can be calculated from the internal standard and the length of the shadow of the silver halide grains.

The silver halide used in the light-sensitive material of the present invention is not particularly limited, and may be, for example, a Research Disclosure.
Osure, hereinafter abbreviated as RD) 308119, page IA, section IA to page 995, section II (production method, halogen composition, crystal habit, monodispersion, latent image forming position, applicable photosensitive material, mixed emulsion, Salt) can be used.

As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additives (chemical sensitizer, spectral sensitizer, supersensitizer, antifoggant, stabilizer, latent image stabilizer, etc.) used in such a process are R
D17643, page 23, section III to page 24, section VI-M, RD1
8716, pages 648 to 649 and RD308119, 9
It is described in page 96, section III-A to page 1000, section VI-M.

Known photographic additives (whitening agents, color image stabilizers, color mixing inhibitors, ultraviolet absorbers, light scattering agents, filter dyes, binders, hardening agents) which can be used in the silver halide emulsion layer according to the present invention. Agents, plasticizers, lubricants, antistatic agents, matting agents, developers, etc.) are also available from RD17643, page 24, section V to page 29, section XX-B, and RD18716, 650 to 65.
1 page, RD308119, page 998 V, page 1011 XX
Those described in -B can be used.

Various couplers can be used in the present invention. Specific examples (Y, M, C couplers, DIR couplers, BAR couplers, colored couplers) are RD
17643, page 25, sections VII-CG, RD30811
9, pp. VII-C, page 1001 and VII-G, page 1002.

The additive used in the present invention is RD3081
19, page 1007, section XIV-A.

In the present invention, the aforementioned RD 17643,
Page 28, section XVII, RD 18716, pages 647-8, and RD
The support described in section 308119, page 1009, XVII can be used.

The light-sensitive materials include the aforementioned RD308119,1
An auxiliary layer such as a filter layer or an intermediate layer described in section VII-K on page 002 can be provided.

The photosensitive material is the same as that of RD308119,
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section VII-K on page 02 can be employed.

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

The light-sensitive material of the present invention is obtained by using
Development can be carried out by the usual methods described in pages 3, 28 to 29, section XIX, RD18716, page 647 and RD308119, pages 1010 to 1011, section XIX.

[0065]

EXAMPLES The present invention will now be described by way of specific examples, which should not be construed as limiting the scope of the present invention.

Example 1 On a cellulose triacetate film support provided with an undercoat layer, each layer having the following composition was sequentially applied from the support side to prepare a comparative sample 101 of a multilayer color photosensitive material.

The amount of addition was 1 m of the coated sample unless otherwise specified.
Indicates the number of grams per ² . In addition, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes (shown by SD) are shown in moles per mole of silver.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

The characteristics of the silver iodobromide emulsion used above are shown in Table 5 (the average grain size is one side length of a cube of the same volume).

[0073]

[Table 5]

Emulsions a, b, f and g were prepared in Japanese Patent Application No. 2000-6.
It was produced with reference to the method for producing Em-1 described in Example of No. 0305.

The above-mentioned sensitizing dyes are added to each of the above emulsions, and after ripening, triphenylphosphine selenide,
Sodium thiosulfate, chloroauric acid, and potassium thiocyanate were added, and chemically sensitized according to a conventional method so as to optimize the fog-sensitivity relationship.

In addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, weight average molecular weight: 10,000 and weight average molecular weight: 100,000
Of two types of polyvinylpyrrolidone (AF-1, AF-
2), inhibitors AF-3, AF-4, AF-5, hardener H
-1, H-2 and the preservative Ase-1 were added.

The structure of the compound used for preparing the sample is shown below. _{SU-1: C 8 F 17} SO 2 N (C 3 H 7) CH 2 COOK SU-2: C 8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3
Br ^- SU-3: bis (2-ethylhexyl) sulfosuccinate ・
Sodium SU-4: sodium tri-i-propylnaphthalenesulfonate AF-3: 1-phenyl-5-mercaptotetrazole AF-4: 1- (4-carboxyphenyl) -5-mercaptotetrazole AF-5: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole AS-1: 2,5-bis (1,1-dimethyl-4-hexyloxycarbonylbutyl) hydroquinone AS-2: dodecyl gallate AS-3: 1,4-bis (2-tetradecyloxycarbonylethyl) piperazine H-1: 1.3-bis (vinylsulfonyl) -i-propanol H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium OIL-1: Tricresyl phosphate OIL-2: dibutyl sebacate ST-1: 4-hydr Carboxymethyl-6-methyl-l, 3,3
a, 7-Tetrazaindene ST-2: Adenine X-1: 5-Ureidohydantoin X-2: Hydantoin PM-2: Polymethyl methacrylate

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Next, Samples 102 to 115 were prepared by changing the sensitizing dye in the twelfth layer and the UV absorber in the thirteenth layer of Comparative Sample 101 as shown in Tables 6 and 7.

For each of the above samples, the maximum sensitivity wavelength {λmax} of the spectral sensitivity distribution of the blue-sensitive layer, 80% of the maximum sensitivity
And the width of the spectral sensitivity distribution at 50% ｛λS (80),
λS (50)｝, the ratio of sensitivity to maximum sensitivity at 400 nm and 480 nm４S (400) / Smax, S (48
0) / Smax｝. The spectral sensitivity distribution was determined as a function of the reciprocal (sensitivity) of the exposure amount giving the minimum density +0.3.

The following tests were performed on each sample. The results are shown in Tables 6 and 7. << Test 1 >> Sensitometry Each sample was subjected to wedge exposure with white light, and processed according to the color development described in paragraphs “0263” to “0270” of JP-A No. 12-63690, and the sensitivity of the blue-sensitive layer was measured. I asked. The sensitivity was represented by the reciprocal of the exposure amount giving a density of fog + 0.3, and was represented by a relative value with the value of sample 101 being 100.

<< Test 2 >> Color Reproducibility Each sample was cut into a 135 size standard, stored in a patrone, loaded into a camera (Konica Hexa: Konica), and held a Macbeth chart in a park under fine weather. A portrait photograph of a woman was taken, subjected to the same color development processing as in Test 1, and dried to obtain a negative film sample.

Each of the developed negative film samples was printed on a color photographic paper (Konica Color Paper QA type A7, manufactured by Konica) using a color printer, and developed (Konica CPK-2-21, manufactured by Konica). And 2 L size color prints were obtained. However, as a printing condition, neutral No. of Macbeth chart is used. 5
Was adjusted so that the color of the color patch became the same as the original.

For each of the obtained color prints, all the colors of the color checker (Macbeth chart) were measured with a colorimeter (CR-200: manufactured by Minolta Camera Co., Ltd.), and the chromatic color 18 of each sample excluding neutral gray was measured.
The sum of the hue angle difference between the color reproduction point and the original was determined.

The Macbeth chart is a Color Rendering Chart manufactured by Macbeth, USA. The hue angle difference (Δhab) is defined by the following equation.

Hue angle (hab): hab = arctan (b ^* / a ^* ) Hue angle difference (Δhab): Δhab = | hab′−hab
Where the hue angle of the Macbeth chart (original) is h
ab, the hue angle of the Macbeth chart reproduced on the color photographic paper is represented by hab '.

The CIE1976 L ^* a ^* b ^* color space is described in, for example, "New Edition of Color Chemistry Handbook 2nd Edition" (1998,
87-130, edited by The Japan Society of Color Science), Chapter 4, color system, etc.

<< Test 3 >> Color Reproducibility Under Fluorescent Light Each sample was processed into 135 size, and a person and an 18% reflection gray cut were photographed under outdoor sunlight using a hexa camera (described above). . Similarly, the same scene was photographed under a fluorescent lamp indoors, and the above color development processing was performed. Using the obtained sample Konica printer NPS-1771,
A color print was obtained by printing on Konica Color Paper QA type A7 (described above). At the time of printing, the scene shot with sunlight was printed so as to be naturally finished, and the scene under indoor fluorescent light was also printed under the same printing conditions. The evaluation was made based on the following criteria as the color of the face of the person of the photographed sample under indoor fluorescent light.

×: Undesirably greenish. Δ: Slightly greenish. ○: Finish almost similar to prints taken in sunlight. ◎: Finish similar to prints taken in sunlight.

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[Table 6]

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[Table 7]

As is clear from Tables 6 and 7, the sample of the present invention has high sensitivity, good color reproducibility, and excellent print performance when photographing under a fluorescent lamp.

Incidentally, the comparative sample 101 and the sample 110 of the present invention were used.
FIG. 2 shows the spectral absorption curve of the blue-sensitive layer.

Example 2 In the sample 110 of Example 1, the emulsion f of the twelfth layer
A color photographic material sample was prepared in the same manner as 110 except that the emulsion was replaced with an emulsion having R (aspect ratio) = 8.5 and an average AgI content of 8.0 mol%.

The obtained samples were evaluated for sensitivity, color reproducibility and suitability for fluorescent lamps in the same manner as in Example 1. still,
The emulsion was prepared by using E described in Examples of Japanese Patent Application No. 2000-60305.
The emulsion was prepared with reference to the emulsion production method of m-2.

A sample prepared using a silver halide emulsion having an aspect ratio of 8 or more exhibited higher sensitivity than the sample of Example 1, and also exhibited excellent performance in color reproducibility and suitability for a fluorescent lamp.

[0102]

According to the present invention, it is possible to provide a silver halide color photographic material having high sensitivity, excellent color reproducibility, and improved color reproducibility under a fluorescent lamp.

[Brief description of the drawings]

FIG. 1A is a schematic view of a high-speed stirring type disperser preferably used in the present invention, and FIG. 1B is a perspective view of an impeller.

2A shows a spectral sensitivity curve of the photosensitive material sample 101 in Example 1 of the present invention, and FIG. 2B shows a spectral sensitivity curve of the blue-sensitive layer of the photosensitive material sample 110 in Example 1. FIG. The horizontal axis is the wavelength (n
m), and the vertical axis indicates relative spectral sensitivity (%).

[Explanation of symbols]

 Reference Signs List 1 tank 2 dissolver 3 vertical axis 4 liquid to be dispersed 5 impeller 6, 7 blades

Claims (4)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic light-sensitive layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-light-sensitive layer on one side on a support. In the above, the blue-sensitive layer has the following general formula (S)
It contains at least one spectral sensitizing dye represented by I) and one spectral sensitizing dye represented by the following general formula (SII), and the spectral sensitivity distribution of the blue-sensitive layer satisfies the following relationship: A silver halide color photographic light-sensitive material comprising: λS (80) ≧ 55 nm λS (50) ≦ 90 nm Here, λS (80) is the maximum sensitivity of the spectral sensitivity distribution of 80.
% Represents the width of the spectral sensitivity distribution, and λS (50) represents the width of the spectral sensitivity distribution at 50% of the maximum sensitivity. Embedded image Wherein Y ₁ is a sulfur atom, a selenium atom or —N (R ₃ ) —
And Y ₂ represents an oxygen atom. Z ₁ and Z ₂ each represent an atomic group necessary to form a benzene ring or a naphthalene ring which may be substituted. R ₁ and R ₂ each represent an aliphatic group, and R ₃ represents a lower alkyl group. X ₁ represents a charge-balancing counter ion, and n1 represents an integer for adjusting the charge of the whole molecule. [Chemical formula 2] [Wherein, Y ₃ and Y ₄ each represent a sulfur atom or a selenium atom. Z ₃ and Z ₄ each represent an atomic group necessary for forming a benzene ring or a naphthalene ring which may be substituted. R ₄ and R ₅ each represent an aliphatic group. X ₂ represents a charge-balancing counter ion, and n2 represents an integer for adjusting the charge of the whole molecule. ] 2. A silver halide color photographic light-sensitive material having a photographic light-sensitive layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-light-sensitive layer on one side on a support. In the above, the blue-sensitive layer is represented by the general formula (S)
The spectral sensitizing dye represented by I) and at least one spectral sensitizing dye represented by the general formula (SII) are contained, and the spectral sensitivity distribution of the blue-sensitive layer satisfies the following relationship. A silver halide color photographic light-sensitive material comprising: λS (80) ≧ 55 nm S (400 nm) ≦ 60% Smax S (480 nm) ≦ 50% Smax Here, λS (80) is the maximum sensitivity of the spectral sensitivity distribution of 80.
% Represents the width of the spectral sensitivity distribution, Smax represents the maximum sensitivity, and S (400 nm) and S (480 nm) represent the sensitivity at 400 nm and 480 nm, respectively. 3. The silver halide color photographic material according to claim 1, wherein the spectral sensitivity distribution of the blue-sensitive layer satisfies the following relationship. 430 nm ≦ λSmax ≦ 455 nm Here, λSmax represents the maximum sensitivity wavelength of the spectral sensitivity distribution. 4. The blue-sensitive layer according to claim 1, wherein said blue-sensitive layer contains silver halide grains having an aspect ratio of 8 or more.
4. The silver halide color photographic light-sensitive material according to 2 or 3.