JP2916803B2 - Spectral sensitized silver halide color photographic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a spectrally sensitized silver halide photographic light-sensitive material, and more particularly, to excellent color reproducibility, particularly excellent in blue-green color reproducibility, and The present invention relates to a silver halide color photographic light-sensitive material having excellent color reproducibility with respect to a light source including a fluorescent light source, and further having excellent stability during production and storage stability of the produced photographic material over time.

[Background of the Invention]

In recent years, the demand for high sensitivity and high image quality of silver halide multilayer color photographic light-sensitive materials has been increasingly strong, and all three major elements of image quality, graininess, sharpness, and color reproducibility, have reached a considerable level. Nevertheless, further improvements in sensitivity and image quality are required.

Among the above three elements, especially regarding color reproducibility,
Although the color purity has improved, the reproducibility of colors, which has been said to be difficult to reproduce in photographs, has not changed much even today. That is, the hue reproducibility is still insufficient. For example, purple-based colors such as violet and bluish-violet, which reflect light of longer wavelengths than 600 nm, or green-based colors such as turquoise and yellow-green, are reproduced in completely different colors from the real thing, disappointing users. Sometimes.

Spectral sensitivity distribution and interlayer effect (inter-image effect, hereinafter referred to as IIE) are major factors related to color reproducibility.
There is.

The following is known about IIE. That is, in a silver halide multilayer color photographic light-sensitive material, it is known to add a compound which forms a development inhibitor or a precursor thereof by coupling with an oxidized color developing agent, and is released from this so-called DIR compound. It is known that, by suppressing the development of other color-forming layers with a development inhibitor, IIE is generated to produce an effect of improving color reproducibility.

In the case of a color negative film, the same effect as IIE can be obtained by using a colored coupler in an amount larger than an amount for canceling unnecessary absorption. However, when color couplers are used extensively, the minimum density of the film increases, which makes it very difficult to judge color / density correction during printing, resulting in poor print color quality. Often happens.

By the way, these techniques contribute to the improvement of color purity among color reproducibility. The so-called diffusive DIR, which has recently been frequently used as a suppressive group or has a large mobility of its precursor, greatly contributes to the improvement of the color purity. However, IIE is difficult to control its directionality and can achieve high color purity, but has the disadvantage of changing the hue. (The control of the direction of IIE is described in US Pat. No. 4,725,529).

On the other hand, regarding the spectral sensitivity distribution, US Pat. No. 3,672,898
The publication discloses an appropriate spectral sensitivity distribution for reducing a variation in color reproducibility due to a difference in light source at the time of photographing. However, this is not a means for improving the aforementioned color having poor hue reproducibility.

Japanese Patent Application Laid-Open No. 61-34541, which discloses a technique combining spectral sensitivity distribution and IIE, has attempted to improve the color in which hue reproduction is difficult with the above-mentioned color film, and has obtained some effects. It seems to be possible. As a typical example, not only the conventional blue-sensitive layer, green-sensitive layer, and IIE from the respective center-of-gravity wavelengths of the red-sensitive layer, but also the IIE from other than the center-of-gravity wavelength of each color-sensitive layer. .

Although this technique seems to be effective to some extent in improving the hue reproducibility of a specific color, specifically, for the development of IIE, in addition to the original blue-sensitive, green-sensitive and red-sensitive photosensitive layers, II
E expression layer and another type of photosensitive silver halide are required,
Due to an increase in the amount of silver and an increase in the number of processes for production,
It has the drawback that the production cost becomes high, and the effect is not sufficient.

For the above reasons, the conventional silver halide color photographic light-sensitive materials have been insufficient in terms of hue reproduction. In particular, with respect to blue-green, it is difficult to faithfully reproduce a color, and a hue far from the actual color may be reproduced.

The present inventors have paid special attention to this blue-green hue reproducibility and as a result of intensive studies, as a result, the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer has been shifted to the shorter wavelength side as a whole to provide the highest sensitivity. It has been found that the above problem can be improved by designing the wavelength λG to be 525 to 560 nm.

However, it has been found that the combination of the above techniques can only provide very unsatisfactory color reproducibility for photographing under fluorescent light or photographing under mixed light of strobe light and fluorescent light. In other words, when the fluorescent light source alone or the strobe light is used but the fluorescent light has an effect, the color reproduction becomes greenish.

On the other hand, as a technique for improving high sensitivity and granularity using silver halide grains, JP-A-57-154232, JP-A-60-138538,
Nos. 61-14636 and 61-245151 disclose so-called core / shell type silver halide grains in which silver iodide is localized inside the grains.

However, in these emulsion techniques, when the surface of silver halide grains constituting the emulsion has a low iodine content and is spectrally sensitized with a sensitizing dye used in the technique, which generally has a tendency not to have strong adsorption, Sufficient color sensitization efficiency cannot be obtained,
Further, the storage stability over time of the produced light-sensitive material was not satisfactory.

Also, JP-A-48-51627 and JP-A-59-77443,
A method of adding a water-soluble iodide to a silver iodobromide emulsion for the purpose of improving color sensitization sensitivity is disclosed.

In this method, although the effect of increasing the adsorptivity of the sensitizing dye to the surface of the silver halide grains to adjust the spectral sensitivity distribution and reducing the desorption of the sensitizing dye under high temperature and high humidity conditions is recognized, If a water-soluble iodide is added until the adsorptivity of the sensitizing dye is sufficiently increased, there is a disadvantage that sensitivity is reduced. Further, in this method, the adsorption reaction of iodide ions on the surface of silver halide grains is extremely fast, and the adsorption is uneven and unstable, so that the obtained emulsion changes its sensitivity over time even when stored in a refrigerator. In many cases, it was difficult to produce a stable quality product.

[Object of the invention]

An object of the present invention is to provide excellent hue reproducibility, particularly hue reproducibility for blue-green, and excellent color reproducibility for light sources including a fluorescent light source, as well as stability during production and storage stability of the produced photosensitive material over time. An object of the present invention is to provide a silver halide color photographic material having excellent sensitivity and high sensitivity.

[Constitution of the Invention] The present inventors have conducted intensive studies in order to develop a silver halide photographic light-sensitive material satisfying such demands.
On the support, at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer (hereinafter, appropriately referred to as "blue-sensitive layer", "green-sensitive layer", and "red-sensitive layer", respectively) Layer) (which may be abbreviated as “layer”), the wavelength λG at which the maximum sensitivity of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer is 525 nm ≦ λG ≦ 560 nm, and The sensitivity SG500 at 500 nm is 1/4 or more of the sensitivity SGmax at the wavelength λG, and at least one of the green-sensitized silver halide emulsions contained in the layer has a halogen composition represented by the following general formula: And a combination of at least one sensitizing dye represented by the general formula [I] and at least one sensitizing dye represented by the general formula [II]. Spectral sensitized ( General formula [I], the [II], the silver halide color light-sensitive material comprising a below) found that the above object can be achieved.

General formula AgCl _a Br _b I _{c wherein} a, b and c satisfy the following conditions.

0 ≦ a <10 ≦ b <10 0 <c ≦ 1 m <c (m: surface iodine composition of the silver halide emulsion to be spectrally sensitized) a + b + c = 1 The present invention is described in more detail below.

In the present invention, the spectral sensitivity distribution refers to 400n
Exposure is performed with spectral light at intervals of several nm from m to 700 nm, the exposure amount that gives a constant density at each wavelength is the sensitivity at each wavelength, and the sensitivity is a function of wavelength.

In the present invention, spectral sensitization is performed by using a combination of at least one sensitizing dye represented by the general formula [I] and at least one sensitizing dye represented by the general formula [II]. The spectral sensitivity distribution of the green-sensitive silver halide emulsion layer has the constitution of the present invention described above.

In the present invention, the sensitivity SG500 at 500 nm has a wavelength λ
The sensitivity is 1/4 or more of the sensitivity SλG in G, and more preferably 1/3 or more.

The spectral sensitivity distribution defined in the present invention is the sensitivity at the minimum density of the green-sensitive layer + an arbitrary density point, and the sensitivity at the minimum density + 0.7 density point is the spectral sensitivity distribution defined by the present invention. If it does, it will appear significantly due to the effects of the present invention.

At least one of the green-sensitive silver halide emulsions contained in the green-sensitive layer of the light-sensitive material of the present invention was formed using fine-grain silver halide having a halogen composition represented by the above general formula. The fine grain silver halide which can be used in the present invention includes silver iodide, silver chloroiodobromide, silver iodobromide and the like, and fine grain silver iodide is preferred.

Regarding the fine grain silver iodide (AgI), generally, cubic γ-AgI and hexagonal β-AgI are known, and the fine AgI used in the present invention may have any crystal structure. Or a mixture thereof.

The grain size of the fine grain silver iodide used in the present invention is preferably 0.2 μm or less, more preferably 0.02 to 0.1.
μm.

Next, the amount of fine silver halide grains added will be described.

When the average grain size of the mother grains, that is, the grains to be grown by adding the fine grain silver halide is d (μm), the amount of the fine grain silver halide grains is not more than 1/100 dmol per mole of the mother grains. It is more preferably in the range of 1 / 20000d to 1 / 300d mol per mol of mother particles, and most preferably 1 / 5000d to 1 / 500d per mol of mother particles.
Is a mole.

The fine grain silver halide used in the present invention preferably has good monodispersibility, and is preferably prepared by a double jet method while controlling the temperature, pH and pAg.

The addition time of the fine grain silver halide in the present invention is preferably any one of the steps from the chemical ripening step to immediately before coating, more preferably the chemical ripening step.

The chemical ripening step referred to here refers to a period from the time when the physical ripening and desalting operations of the mother particles are completed to the time when an operation for stopping the chemical ripening is performed after adding the chemical sensitizer. . As a method for terminating the chemical ripening, a method of lowering the temperature, a method of lowering the pH, a method of using a chemical ripening terminator, and the like are known. The method used is preferred.
Examples of the chemical ripening inhibitor include halides (eg, potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (eg, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene)
It has been known. These are used alone or in combination of a plurality of compounds.

Further, the addition of the fine grain silver halide of the present invention may be carried out several times at intervals, or after addition of the fine grain silver halide, another chemically ripened emulsion may be further added. .

The temperature of the mother grain emulsion when adding the fine grain silver halide is preferably in the range of 30 to 80 ° C, more preferably 40 to 65 ° C.
Is particularly preferred.

In addition, the present invention is preferably carried out under the condition that part or all of the fine grain silver halide to be added disappears immediately before the coating and immediately before coating, more preferably 20% of the added fine grain silver halide. The above is the disappearance immediately before the application.

The amount of disappearance was determined by centrifuging the emulsion or coating solution after the addition of the fine silver halide particles under appropriate conditions, measuring the absorption spectrum of the supernatant, and measuring the absorption of the known concentration of the fine silver halide liquid. This can be done by comparing with a spectrum.

In the present invention, in order to spectrally sensitize at least one kind of the silver halide emulsion spectrally sensitized to green sensitivity, at least one kind of a sensitizing dye represented by the following general formula [I] and the following general formula [I] At least one of the sensitizing dyes represented by formula (II) is used in combination (hereinafter, the sensitizing dyes represented by formula (I) and formula (II) are also referred to as sensitizing dyes of the present invention).

In the formula, R ¹ , R ² , R ⁴ and R ⁵ each represent an alkyl group or an alkenyl group. R ³ represents a hydrogen atom, an aryl group or an alkyl group. X ^1, X ² represents a charge balancing counter ion, n _1,
n ₂ represents the value necessary to neutralize the 0 or more molecules overall charge. Z ¹ and Z ² each represent an atomic group necessary for forming a benzoxazole nucleus or a naphthoxazole nucleus.

Z ³ and Z ⁴ are a pyrroline nucleus, a pyridine nucleus, a quinoline nucleus, an indolenine nucleus, a benzimidazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, and a selenazole, respectively. Represents the group of atoms required to complete the nucleus, benzoselenazole nucleus, or naphthoselenazole nucleus.

 The sensitizing dye of the present invention will be described more specifically.

In the compounds represented by the general formulas [I] and [II] used in the present invention, R ¹ , R ² , R ⁴ and R ⁵ each represent a branched or straight-chain alkyl having 1 to 10 carbon atoms. Groups (eg, methyl, ethyl, propyl, butyl, pentyl, i-pentyl, 2-ethyl-hexyl, octyl, decyl, etc.)
Or an alkenyl group having 3 to 10 carbon atoms (eg, 2-propenyl, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1-methyl-3-butenyl, 4-
Hexenyl). These groups include a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkoxy group (eg, methoxy, ethoxy, etc.), an aryloxy group (eg, phenoxy, p-tolyloxy, etc.), a cyano group, a carbamoyl group (eg, carbamoyl, N -Methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.), sulfamoyl group (eg, sulfamoyl, N, N-3-oxapentamethyleneammonosulfonyl, etc.), methanesulfonyl group, alkoxycarbonyl group (eg, ethoxycarbonyl, butoxycarbonyl) ), An aryl group (eg, phenyl, carboxyphenyl, etc.), an acyl group (eg, acetyl, benzoyl, etc.), an acylamino group (eg, acetylamino, benzoylamino, etc.), a sulfonamide group (eg, methanesulfonamide, butanesulfone) It may be substituted with a substituent bromide, etc.) or the like, preferably water-soluble group (e.g. sulfo group, carboxyl group, phosphono group, sulfato group, a hydroxyl group, such as a sulfino group)
Is replaced by Examples of the alkyl group substituted with the water-soluble group represented by R ¹ and R ² include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, hydroxyethyl, carboxyethyl, 3-sulfinobutyl, -Phosphonopropyl, p-sulfobenzyl, o-carboxybenzyl and the like. Examples of the alkenyl group substituted with a water-soluble group include 4-sulfo-3-butenyl and 2-carboxy-2-propenyl. .

In the general formula [I], it is preferable that ^one of R ¹ and R ² has a water-soluble group.

The ion for canceling the intramolecular charge represented by X ¹ and X ² is selected from an anion and a cation. The anion includes inorganic and organic ones, specifically, a halogen ion (for example, each ion such as chloro, bromine, and iodine) and an organic acid anion (for example, p-toluenesulfonate, p-chlorobenzenesulfonate, methanesulfonate, and the like) Ion), tetrafluoroboron ion, perchlorate ion, methyl sulfate ion, ethyl sulfate ion and the like.

The cations include inorganic and organic cations, specifically, hydrogen ions, alkali metal ions (eg, lithium, sodium, allium, cesium, etc.), and alkaline earth metal ions (eg, magnesium, calcium, strontium, etc.). Ion), ammonium ion, and organic ammonium ion (for example, each ion such as trimethylammonium, triethylammonium, tripropylammonium, triethanolammonium, and pyridinium).

The benzoxazole nucleus represented by Z ¹ and Z ² includes those having a substituent on the ring. Specific examples of the substituent on the ring include a halogen atom (eg, chlorine, bromine, fluorine, etc.) and an alkyl group having 6 or less carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, etc.)
Aryl group (eg, phenyl group), alkoxy group having 4 or less carbon atoms (eg, methoxy group, ethoxy group, butoxy group, etc.) aryloxy group (eg, phenoxy group, etc.)
An acyl group having 6 or less carbon atoms (such as an acetyl group, a propionyl group, or a benzoyl group); an alkoxycarbonyl group having 8 or less carbon atoms (such as a methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, or a benzyloxycarbonyl group); Examples include a cyano group and a trifluoromethyl group.

Z ³ and Z ⁴ are each a pyrroline nucleus, a pyridine nucleus, a quinoline nucleus, an indolenine nucleus, a benzimidazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, The group of atoms necessary to complete the selenazole nucleus, benzoselenazole nucleus, or naphthoselenazole nucleus is shown, and the above heterocyclic nucleus includes those having a substituent on the ring. As a substituent on the ring,
The same substituents as described in the description of the heterocyclic nucleus represented by Z ¹ and Z ² can be mentioned.

Of the heterocyclic nuclei represented by Z ³ and Z ⁴ , preferred is
Benzothiazole, naphtho (2,1-d) thiazole, naphtho (2,3-d) thiazole, benzoxazole, naphtho (2,1-d) oxazole, naphtho (2,3-d) oxazole System, benzoselenazole system,
Naphtho (2,1-d) selenazole, naphtho (2,3-d)
Selenazole and quinoline nuclei.

Specific examples of the sensitizing dyes represented by the general formulas [I] and [II] are shown below, but the sensitizing dyes used in the present invention are not limited to these compounds.

The sensitizing dyes represented by the general formulas (I) and (II) according to the present invention include, for example, Journal of the American
Chemical Society, (J. Am. Chem. Soc.), 67 , 1
875-1899 (1945)) by FM Hammer, The
The Chemistry of Heterocyclic Compounds # 18
Volume, The Cyanine Dyes and Related Compound
s) (A. Weissherger ed. Interscience, New York 1
964), U.S. Pat.Nos. 3,483,196, 3,541,089, 3,5
98,595, 3,598,596, 3,632,808, 3,757,66
The person skilled in the art can easily synthesize by referring to the method described in JP-A-60-78445 and the specification of JP-A No. 60-78445.

The optimum concentration of the sensitizing dyes of the general formulas [I] and [II] can be determined by a method known to those skilled in the art. For example, there is a method in which a certain emulsion is divided, sensitizing dyes having different concentrations are contained in each emulsion, and the performance is determined by measuring the performance of each emulsion.

The addition amount of the sensitizing dye in the present invention is not particularly limited, but may be 2 × 10 ⁻⁶ mol to 1 × per mol of silver halide.
It is preferable to use 10 ⁻² mol, and it is more preferable to use 5 × 10 ₋₆ mol to 5 × 10 ₋₃ mol.

For the addition of the sensitizing dye to the emulsion, a method well known in the art can be used. For example, these sensitizing dyes can be dispersed directly in the emulsion or dissolved in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide or a mixture thereof. Or diluted with water or dissolved in water,
These solutions can be added to the emulsion. Ultrasonic vibration can be used during the dissolution process. Further, as described in U.S. Pat.No. 3,469,937, the dye is prepared by dissolving the dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding the dispersion to an emulsion.
As described in JP-B-46-24185 and the like, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion is also used. The dye can be added to the emulsion in the form of a dispersion by an acid dissolution dispersion method. For addition to the emulsion, the methods described in U.S. Pat. Nos. 2,912,345, 3,342,605, 2,996,287 and 3,425,835 can be used. The general formula [I] used in the present invention,
The sensitizing dye represented by the formula [II] can be added to the emulsion at any time during the production process from the time when silver halide grains are formed to the time immediately before coating on a support.

Specifically, before the formation of silver halide grains, during the formation of silver halide grains, from the end of the formation of silver halide grains to the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, during chemical sensitization, Any time selected from the time of termination and from the end of chemical sensitization to the time of coating may be used. It may be added plural times. The order of addition of the stabilizer and the antifoggant does not matter, but it is preferably added at the time of particle formation or chemical ripening, that is, at a step before the preparation of the coating solution. As a method for adding the sensitizing dyes represented by the general formulas [I] and [II], the respective sensitizing dyes are dissolved in the same or different solvents, and these solutions are mixed prior to addition to the emulsion. Alternatively, they may be separately added to the emulsion, but it is more preferable to add them after mixing the solution prior to addition to the emulsion.

The sensitizing dye used in the present invention can be used in combination with another sensitizing dye.

The sensitizing dye used in the present invention may be used in combination with a compound having a supersensitizing effect.

In the present invention, when at least one sensitizing dye represented by the general formula [I] and at least one sensitizing dye represented by the general formula [II] are used, the reflection spectrum of the spectrally sensitized emulsion is used. And the absorption maximum observed when the sensitizing dye contained in the emulsion alone is adsorbed to silver halide grains having the same halogen composition and crystal habit as contained in the emulsion alone. A distance of 5 nm or more from any of the absorption maximums in the reflection spectrum is preferable because the wavelength region to be constituted in the present invention is supersensitized and spectrally sensitized.
More preferably, the difference between the wavelengths is 7 nm or more, and it is particularly preferable that the difference is 10 nm or more.

In the present invention, the reflection spectrum of the emulsion is measured, for example, by the following method.

A general photographic additive such as a surfactant and a hardening agent is added to the emulsion of the present invention to prepare a coating solution, which is coated on a triacetyl cellulose support, dried, and dried. create. The reflection spectrum of the prepared sample can be measured using an ordinary spectrophotometer (for example, Hitachi Model U-3210 Hitachi Automatic Recording Spectrophotometer) equipped with an integrating sphere.

In the present invention, the general formula (III), the general formula (I
V], and the use of at least one sensitizing dye represented by the general formula [V] further enhances green light sensitivity, which is a preferred embodiment.

In the formula, Z ⁵ and Z ⁶ represent an atomic group necessary for forming a benzimidazole nucleus, and Z ⁷ and Z ⁸ represent an atomic group necessary for forming a naphthoxazole nucleus. Z ⁹ represents an atomic group necessary for forming a benzoxazole nucleus, Y represents a sulfur or selenium atom, and Z ¹⁰ represents a benzothiazole nucleus or a benzoselenazole nucleus. R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R
¹³ and R ¹⁴ have the same meanings as R ¹ and R ^{2 in} formula [I], and R ¹² and R ^14
15 has the same meaning as R ³ , X ³ , X ⁴ , and X ⁵ have the same meanings as X ¹ and X ² , and n ₃ , n ₄ , and n ₅ have the same meanings as n ₁ and n ₂ . R ⁸ and R ⁹ represent an alkyl group, an alkenyl group or an aryl group. Z ⁷ , Z ⁸ ,
The heterocyclic nuclei represented by Z ⁹ and Z ¹⁰ include those having the same substituent on the ring as described for Z ¹ and Z ² .

Examples of the alkyl group and alkenyl group represented by R ⁸ and R ⁹ include groups similar to those described in the description of R ¹ and R ² , and examples of the aryl group include a phenyl group.

The benzimidazole nucleus represented by Z ⁵ or Z ⁶ includes those having a substituent on the ring. Specific examples of the substituent on the ring include the following.

Examples of the acyloxy group include groups such as acetoxy and propionoxy; examples of the alkoxycarbonyl group include groups such as methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl; examples of the aryloxycarbonyl group include phenoxycarbonyl and tolyloxy. There are groups such as carbonyl, β-natoxycarbonyl and the like, and as the halogen atom, for example, chlorine,
There are bromine, iodine, fluorine and the like, acyl groups include groups such as acetyl, propionyl and benzoyl, and alkylsulfonyl groups such as methylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl and groups such as ethylsulfonyl And the arylsulfonyl group includes, for example, phenylsulfonyl, p
-A group such as tolylsulfonyl; examples of the carbamoyl group include groups such as carbamoyl and N-methylcarbamoyl; and examples of the sulfamoyl group include sulfamoyl, N-methylsulfamoyl, morpholinosulfonyl, and piperidinosulfonyl. The group of is mentioned. Examples of the perfluorohydrocarbon group include groups such as a perfluorobutyl group and a perfluorophenyl group.

Specific examples of the sensitizing dyes represented by the general formulas (III), (IV) and (V) are shown below, but the sensitizing dyes used in the present invention are not limited to these compounds. Absent.

The general formulas [III], [IV] and [V] according to the present invention.
The sensitizing dye represented by is similar to the sensitizing dyes represented by the above formulas [I] and [II], and can be easily synthesized by those skilled in the art.

As a method of adding the dye represented by the general formulas [III], [IV] or [V], the respective sensitizing dyes are the same as or different from the sensitizing dyes represented by the general formulas [I] and [II]. These solutions may be dissolved in a solvent and mixed with these solutions prior to addition to the emulsion, or may be separately added to the emulsion.

A preferred method is to mix the solutions of the sensitizing dyes represented by the general formulas [I] and [II] prior to addition to the emulsion. A part of the sensitizing dye may be divided and used alone or in the formulas [III], [I
V] or a sensitizing dye represented by [V]. It is also preferable to add a sensitizing dye represented by the general formula [I] or [II] and a sensitizing dye represented by the general formula [III], [IV] or [V] to the emulsion as a mixed solution. .

The silver halide emulsion used in the color photographic light-sensitive material of the present invention can be chemically sensitized by a conventional method.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous (but not limited to) to use gelatin as a binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer.

The present invention can be preferably applied to a color negative film, a color reversal film, and the like.

A color-forming coupler is generally used in the emulsion layer of the color photographic light-sensitive material of the present invention.

Coupling with colored couplers, competing couplers, and oxidized developing agents, which have the effect of correction, further enhances development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents, hardeners, and fog. Chemicals that release photographically useful fragments, such as agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers, can optionally be used.

Photosensitive materials include filter layers, antihalation layers,
An auxiliary layer such as an irradiation prevention layer can be provided. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained.

To the light-sensitive material, a formalin scavenger, a fluorescent brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder and a bleaching accelerator can be added.

As the support, any material such as paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate and the like can be used.

In order to obtain a dye image using the color light-sensitive material of the present invention, a generally known means of performing color photographic processing after exposure can be used.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

In all the following examples, the addition amount of the silver halide photographic light-sensitive material particularly shows the number of grams per 1 m ² unless otherwise noted. Further, silver halide and colloidal silver are shown in terms of silver.

Emulsion Production Example 1 Silver iodobromide emulsions I to C shown in Table 1 were prepared according to the method described in JP-A-60-138538.

Next, an aqueous solution containing 5% by weight of ossein gelatin is added to the reaction vessel, and while stirring at 40 ° C., a 3.5N silver nitrate aqueous solution and
Silver iodide fine particles (A) were prepared by adding 1 mol of each 3.5N potassium iodide aqueous solution for 30 minutes at a constant rate. At this time, the pAg during the addition was kept at 13.5 by a conventional pAg control means.

The resulting silver iodide has β-AgI and γ with an average grain size of 0.06 μm.
-AgI mixture.

Silver iodobromide emulsions I to C were each optimally chemically ripened using sodium thiosulfate, chloroauric acid and ammonium thiocyanate.

The chemical ripening terminator used was 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene.

In this chemical ripening step, fine grain silver iodide or a comparative compound was added to prepare a chemically ripened emulsion according to the present invention and a comparative emulsion.

 Table 2 shows the production conditions and the like of the prepared emulsion.

Example 1 (Preparation of Samples No. 101 to No. 104) On a triacetylcellulose film support, layers having the following compositions were sequentially formed from the support side. No.104 was created.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-1) 0.20 Colored coupler (CC-1) 0.02 High boiling solvent (Oil-1) 0.20 High boiling solvent (Oil-2) 0.20 Gelatin 1.6 Second layer; Intermediate layer (IL-1) Gelatin 1.3 Third layer: Red-sensitive emulsion layer (R) Silver iodobromide emulsion (Em-1) 0.4 Silver iodobromide emulsion (Em-2) 0.3 Sensitizing dye (S-2) 3.4 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) 3.2 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 0.50 Cyan coupler (C- 2) 0.13 Colored cyan coupler (CC-1) 0.07 DIR compound (D-1) 0.006 DIR compound (D-2) 0.01 High boiling solvent (Oil-1) 0.55 Gelatin 1.0 Fourth layer; Intermediate layer (IL-2) Gelatin 0.8 fifth layer; green-sensitive emulsion layer (G) Silver iodobromide emulsion described in column A of Table-3 0.6 Silver iodobromide emulsion described in column B of table-3 0.2 mazen Coupler (M-1) 0.6 Colored magenta coupler (CM-1) 0.10 DIR compound (DIR-19) 0.02 High boiling solvent (Oil-2) 0.70 Gelatin 1.0 6th layer; Yellow filter layer (YC) Yellow colloidal silver 0.05 added Additive (HS-1) 0.07 Additive (HS-2) 0.07 Additive (SC-1) 0.12 High boiling solvent (Oil-2) 0.15 Gelatin 1.0 7th layer; Blue-sensitive emulsion layer (B) Silver iodobromide emulsion (Em-3) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S-10) 5.8 × 10 ^-4 (mole / silver 1 mol) Yellow coupler (Y-2) 0.38 DIR compound (D- 1) 0.003 DIR compound (D-2) 0.006 High boiling solvent (Oil-2) 0.18 Gelatin 1.3 Eighth layer; First protective layer (PRO-1) Silver iodobromide emulsion (Em-4) 0.3 UV absorber ( UV-1) 0.07 UV absorber (UV-2) 0.1 Additive (HS-1) 0.2 Additive (HS-2) 0.1 High boiling solvent (Oil-1) 0.07 High boiling Medium (Oil-3) 0.07 Gelatin 0.8 Ninth layer; Second protective layer (PRO-2) Alkali-soluble matting agent (Average particle size 2 μm) 0.13 Polymethyl methacrylate (Average particle size 3 μm) 0.02 Gelatin 0.5 Is a coating aid, a dispersion aid, in addition to the above composition,
Hardeners and dyes were added as appropriate.

Em-1: average silver iodide content 7.5 mol%, average grain size 0.55 μm Em-2: average silver iodide content 2.5 mol%, average grain size 0.36 μm Em-3: average silver iodide content 7.5 mol %, Average grain size: 0.65 μm Em-4: average silver iodide content: 2.0 mol%, average grain size: 0.08 μm Each sample was subjected to the following exposure and processed in the following processing steps.

(I) Wedge exposure using a white light source (ii) Wedge exposure using a three-wavelength fluorescent light source as the same light amount as the light source of (i) (iii) Wedge exposure using 480 nm to 600 nm every 2 nm spectrum light source Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixed 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the processing solution used in each processing step is shown below. Show.

Color developing solution 4-Amino-3-methyl-N- (β-hydroxyethyl) -aniline / sulfate 4.75 g Sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2.0 g 37.5 g of anhydrous calcium carbonate 1.3 g of potassium bromide Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1.

Bleaching solution Iron ammonium salt of ethylenediaminetetraacetate 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to adjust the pH to 1, and adjust the pH to 6.0 using aqueous ammonia.

Fixing solution Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to make 1 and adjust to pH 6.0 with acetic acid.

Stabilizing solution Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1

The results are summarized in Table-3.

As is clear from Table 3, the sample according to the present invention has improved storage stability over time and suitability for fluorescent lamps without impairing the sensitivity. Further, Sample No. 107 to which the dye represented by the general formula [V] is further added has higher sensitivity than a sample to which no dye is added, and it is understood that this is a more preferable embodiment.

Example 2 (Preparation of Samples Nos. 201 to 205) On a triacetylcellulose film support, layers having the following compositions were sequentially formed from the support side. It was created.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-1) 0.20 Colored coupler (CC-1) 0.02 High boiling solvent (Oil-1) 0.20 High boiling solvent (Oil-2) 0.20 Gelatin 1.6 Second layer; Intermediate layer (IL-1) Gelatin 1.3 Third layer; Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.4 Silver iodobromide emulsion (Em-2) 0.3 Sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver mol) Cyan coupler (C-1) 0.50 Cyan coupler (C-2) 0.13 Colored cyan coupler (CC-1) 0.07 DIR compound (D-1) 0.006 DIR compound (D-2) 0.01 high boiling solvent (Oil-1) 0.55 gelatin 1.0 4th layer; high sensitivity red-sensitive emulsion layer (RH) silver iodobromide emulsion (Em-3) 0.9 sensitizing dye (S-1) 1 0.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-2) 0.23 Colored cyan coupler (CC-1) 0.03 DIR compound (D-2) 0.02 High boiling solvent (Oil-1) 0.25 Gelatin 1.0 Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 sixth layer; low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion spectrally sensitized to green-sensitivity described in column A of Table-4 0.6 Green-sensitivity described in column B of table-4 Silver iodobromide emulsion spectrally sensitized to 0.2 magenta coupler (M-1) 0.17 magenta coupler (M-2) 0.43 colored magenta coupler (CM-1) 0.10 DIR compound (D-3) 0.02 high boiling solvent ( Oil-2) 0.70 gelatin 1.0 7th layer; high sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion spectrally sensitized to green sensitivity described in column C of Table-4 0.9 Magenta coupler (M-1) 0.03 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.04 DIR compound (D-3) 0.004 High boiling solvent (Oil-2) 0.35 Gelatin 1.0 Eighth layer; Yellow filter Layer (YC) Yellow colloidal silver 0.1 Additive (HS-1) 0.07 Additive (HS-2) 0.07 Additive (SC-1) 0.12 High boiling solvent (Oil-2) 0.15 Gelatin 1.0 Ninth layer; Low sensitivity blue Sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.60 Yellow coupler (Y-2) 0.32 DIR compound (D-1) 0.003 DIR compound (D-2) 0.006 High boiling solvent (Oil-2) 0.18 Gelatin 1.3 10th layer; High sensitivity blue Sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-5) 0.5 Sensitizing dye (S-10) 3.0 × 10 ^-4 (mol / Silver 1 mol) Sensitizing dye (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 Yellow coupler (Y-2) 0.10 High boiling solvent (Oil-2) 0.05 gelatin 1.0 11th layer; 1st protective layer (PRO-1) Silver iodobromide emulsion (Em-4) 0.3 UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.1 Additive (HS-1) 0.2 Additive (HS-2) 0.1 High boiling solvent (Oil-1) 0.07 High boiling solvent (Oil-3) 0.07 Gelatin 0.8 12th layer; 2nd protective layer (PRO-2) Alkali-soluble matting agent ( (Average particle size 2 μm) 0.13 Polymethyl methacrylate (Average particle size 3 μm) 0.02 Gelatin 0.5 In addition to the above composition, each layer has a coating aid SU-2, a dispersion aid SU-1, and a hardener H-1. , H-2, dyes AI-1 and AI-2 were added as appropriate.

The emulsion used in the above sample is an internal high iodine type monodisperse emulsion shown below.

Em-1: average silver iodide content 3.5 mol%, average grain size 0.55 μm Em-2: average silver iodide content 2.5 mol%, average grain size 0.36 μm Em-3: average silver iodide content 7.5 mol Em-4: average silver iodide content 2.0 mol%, average grain size 0.08 μm Em-5: average silver iodide content 8.5 mol%, average grain size 1.02 μm The hue reproducibility of the green cloth and the stability of the manufactured sample during manufacture were evaluated.

 Each sample was subjected to the same treatment as in Example 1.

As is evident from Table 4, the sample of the present invention is excellent in stability at the time of production and has good blue-green color reproduction.

 The structures of the compounds used in Examples 1 and 2 are shown below.

Emulsion Production Example 2 The following emulsion was prepared according to the method described in Japanese Patent Application No. 63-224002.

Em-d: average particle size 0.27 μm, average iodine composition 8.0 mol%,
A core / shell emulsion having a surface iodine composition of 0.5 mol% Em-e: an average grain size of 0.38 μm, an average iodine composition of 8.5 mol%,
Core / shell emulsion having a surface iodine composition of 0.1 mol% The above silver iodobromide emulsion was optimally chemically sensitized using sodium thiosulfate, chloroauric acid and ammonium thiocyanate.

Also, as a terminator for chemical ripening, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene was used.

In this chemical ripening step, the same fine grain silver iodide (A) or a comparative compound as used in Example 1 was added to prepare a chemical ripening agent emulsion and a comparative emulsion of the present invention. Table 5 shows the emulsions and the production conditions.

Example 3 Layers having the following compositions were sequentially formed on a triacetyl cellulose film support from the support side to prepare multilayer color photographic light-sensitive material samples No. 301 to 305.

First layer; Anti-halation layer Black colloidal silver 0.20 UV absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.20 Gelatin 1.40 Second layer; Intermediate layer Gelatin 1.30 Third layer; Low sensitivity red-sensitive emulsion layer High iodine silver iodobromide emulsion (average iodine composition 8.0 mol%, average grain size 0.27 μm) 0.80 sensitizing dye (SD-1) 3.0 × 10 ^-4 sensitizing dye (SD-2) 4.0 × 10 ^-4 Cyan coupler (C-1) 0.45 Colored cyan coupler (CC-1) 0.06 DIR compound (D-1) 0.05 High boiling solvent (Oil-1) 0.50 Gelatin 0.90 4th layer; Intermediate layer Gelatin 1.00 5th layer; High sensitivity Red-sensitive emulsion layer Internal high iodine silver iodobromide emulsion (average iodine composition 8.5 mol%, average grain size 0.38 μm) 1.20 sensitizing dye (SD-1) 2.5 × 10 ^-4 sensitizing dye (SD-2) 3.5 × 10 ^-4 cyan coupler (C-1) 0.15 colored cyan coupler (CC-1) 0.02 DIR compound (D-1) 0.08 high boiling point solvent (Oil-1) 0.25 Gelatin 0.90 6th layer; Intermediate layer Color stain inhibitor (SC-1) 0.10 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00 7th layer; Low sensitivity green-sensitive emulsion layer Silver iodobromide emulsion described in Table-6 0.80 Magenta coupler (M-1) 0.53 Colored magenta coupler (CM-1) 0.09 DIR compound (D-2) 0.01 DIR compound (D-3) 0.03 High boiling solvent (Oil-2) 0.70 Gelatin 1.30 Eighth layer; High Sensitive green-sensitive emulsion layer Silver iodobromide emulsion described in Table-6 0.90 Magenta coupler (M-1) 0.17 Colored magenta coupler (CM-1) 0.06 DIR compound (D-2) 0.04 DIR compound (D-3) 0.01 High Boiling point solvent (Oil-2) 0.40 Gelatin 0.80 9th layer; Yellow filter layer Yellow colloidal silver 0.10 Color stain inhibitor (SC-1) 0.10 High boiling point solvent (Oil-2) 0.10 Gelatin 1.00 10th layer; Low sensitivity blue sensitivity Emulsion layer Internal high iodine silver iodobromide emulsion (average iodine composition 8.0 mol%, average particle size 0.27 μm) 0.50 Sensitizing dye (SD-6) 8.0 × 10 ^-4 Yellow coupler (Y-1) 0.95 DIR compound (D-1) 0.05 High boiling solvent (Oil-2) 0.10 Gelatin 0.50 11th layer; high-sensitivity blue-sensitive emulsion layer Internal high iodine silver iodobromide emulsion (average iodine composition 8.5 mol%, average particle size 0.38 μm) 0.50 sensitizing dye (SD-6) 6.0 × 10 ^-4 yellow Coupler (Y-1) 0.20 DIR compound (D-1) 0.01 High boiling solvent (Oil-2) 0.02 Gelatin 0.40 12th layer; 1st protective layer Fine grain silver iodobromide (average particle size 0.08 μm) 0.20 UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.10 High boiling solvent (Oil-1) 0.07 High boiling solvent (Oil-3) 0.07 Gelatin 0.60 13th layer; 2nd protective layer Alkali-soluble matting agent (average particle 0.15 polymethyl methacrylate (average particle size 3 μm) 0.04 Slip agent (WAX-1) 0.04 Gelatin 0.60 Example 3 below 1 shows the structure of the compound used.

In addition, in addition to the above composition, a coating aid Su-1, a dispersion aid Su-2,
Viscosity adjusters, hardeners H-1, H-2, stabilizer ST-1, antifoggant AF-1, two types: 100,000 and 1,100,000
AF-2 was added.

The obtained sample was evaluated for sensitivity, storage stability with time and color reproducibility of a blue-green cloth in the same manner as in Examples 1 and 2. However, the sensitivity is a relative value when the sensitivity of sample No. 301 is 100.

As is clear from Table 6, the sample of the present invention has good blue-green color reproducibility, and is excellent in both sensitivity and storage stability with time.

〔The invention's effect〕

According to the present invention, color reproducibility, particularly excellent color reproducibility for blue-green, and excellent color reproducibility for light sources including a fluorescent light source, and stability during production, storage stability over time of the produced photosensitive material. An excellent silver halide color photographic light-sensitive material having high sensitivity has been provided.

Continuation of the front page (51) Int.Cl. ⁶ identification symbol FI G03C 7/392 G03C 7/392 B (56) References JP-A-64-19346 (JP, A) JP-A-1-237654 (JP, A JP-A-62-160448 (JP, A) JP-A-2-191937 (JP, A) JP-A-2-201350 (JP, A) JP-A-2-213837 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) G03C 7 / 20,7 / 26 G03C 7 / 392,1 / 015 G03C 1 / 16,1 / 18

Claims (1)

(57) [Claims] A silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. The wavelength λG giving the highest sensitivity of the spectral sensitivity distribution of the sensitive silver halide emulsion layer is 525 nm ≦ λG ≦ 560 nm, and the sensitivity SG500 at 500 nm is 1/4 or more of the sensitivity SGmax at the wavelength λG, and is included in the layer. At least one kind of silver halide emulsion spectrally sensitized to green sensitivity is formed using a fine grain silver halide having a halogen composition represented by the following general formula, and the sensitized silver halide emulsion represented by the following general formula [I] A silver halide color light-sensitive material characterized by being spectrally sensitized using a combination of at least one kind of a sensitizing dye and at least one kind of a sensitizing dye represented by the following general formula [II]. General formula AgCl _a Br _b I _{c wherein} a, b and c satisfy the following conditions. 0 ≦ a <10 0 ≦ b <10 0 <c ≦ 1 m <c (m: composition of surface iodine of silver halide emulsion to be spectrally sensitized) a + b + c = 1 In the formula, R ¹ , R ² , R ⁴ and R ⁵ each represent an alkyl group or an alkenyl group. R ³ represents a hydrogen atom, an aryl group or an alkyl group. X ¹ and X ² represent a charge-matching counter ion, and n ₁ and n ₂
Represents a value required to neutralize the charge of the whole molecule of 0 or more. Z ¹ and Z ² each represent an atomic group necessary for forming a benzoxazole nucleus or a naphthoxazole nucleus. Z ³ and Z ⁴ are a pyrroline nucleus, a pyridine nucleus, a quinoline nucleus, an indolenine nucleus, a benzimidazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, and selenazole, respectively. Represents the group of atoms required to complete the nucleus, benzoselenazole nucleus, or naphthoselenazole nucleus