JPH08234385A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide color photographic sensitive material with low fog and high sensitivity which is excellent in the shelf life against the lapse of time of the manufactured photosensitive material. CONSTITUTION: In the silver halide color photographic sensitive material having at least one photographic constituting layer on a support body, at least one layer of the photographic constituting layers contains a sensitizing pigment represented by the formula I (R11 and R12 each represent an alkyl group, an alkenyl group, or an alkynyl group, R13 represents hydrogen atom, an alkyl group, or an aryl group, Z11 represents a benzoxazole nucleus forming atomic group, Z12 represents a benzothiazole nucleus or benzoselenazole nucleus forming atomic group, Z represents a charge-equilibrated pair ion, n1 represents the charge adjusting value of the whole molecule) and a coupler represented by the formula II (R21 represents hydrogen atom or substituent, R22 represents chlorine atom or an alkoxyl group, R22 represents a substituent, n2 represents an integer of 1-5, and R24 , R25 , R26 , R27 and R28 each represent hydrogen atom or a halogen atom).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spectrally sensitized silver halide color photographic light-sensitive material. More specifically, the manufactured light-sensitive material has excellent stability during storage and has a spectral sensitivity in the green wavelength region. It relates to an enhanced silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, performance demands on silver halide color light-sensitive materials for photography have become more and more severe, and higher levels of photographic characteristics such as sensitivity, fog and graininess and storability have been achieved. There is a demand. Particularly in recent years, with the spread of compact zoom cameras and lens-equipped films that are generally single-use cameras, high sensitivity has become an essential requirement for photographic light-sensitive materials.

Three primary colors of subtractive color are used for silver halide color photographic light-sensitive materials, and a color image is formed by a combination of three dyes derived from a yellow coupler, a magenta coupler and a cyan coupler. As a magenta coupler used in a conventional silver halide color photographic light-sensitive material, a pyrazolone, a pyrazolinobenzimidazole or an indanone coupler is known. Among them, U.S. Pat.Nos. 2,439,098, 2,369,489 and 3,558,
Various 5-pyrazolone derivatives described in, for example, No. 319, No. 2,311,081, No. 3,677,764, British Patent No. 1,173513, and JP-A No. 52-80027 are widely used.

As a means for spectrally sensitizing the green wavelength region of a silver halide emulsion, a technique using oxacarbocyanine or benzimidazolocarbocyanine is known as described in JP-A-61-286845. There is.

However, these conventional techniques cannot be said to be sufficiently satisfactory in terms of sensitivity, fog and storability of the manufactured light-sensitive material, and improvements have been desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having low fog, high sensitivity and excellent storability of the manufactured light-sensitive material over time.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention provide a silver halide color photographic light-sensitive material having at least one photographic constituent layer on a support, and in at least one of the photographic constituent layers, the following general formula [ The above object is achieved by a silver halide color photographic light-sensitive material characterized by containing at least one sensitizing dye represented by the formula I] and at least one coupler represented by the following general formula [MI]. I found that.

General formula [I]

[0009]

[Chemical 4]

In the formula, R ₁₁ and R ₁₂ represent a substituent selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group and a substituted or unsubstituted alkynyl group, and R ₁₃ represents a hydrogen atom or a substituted group. Or, represents an unsubstituted alkyl group or a substituted or unsubstituted aryl group. Z ₁₁ represents an atomic group necessary for forming a substituted or unsubstituted benzoxazole nucleus, Z ₁₂ represents a substituted or unsubstituted benzothiazole nucleus,
Represents a group of atoms necessary to form either a substituted or unsubstituted benzoselenazole nucleus. X represents a charge-balancing counterion, and n ₁ represents a numerical value for controlling the charge of the whole molecule.

General formula [M-I]

[0012]

Embedded image

In the formula, R ₂₁ represents a hydrogen atom or a substituent, and R ₂₂ represents a chlorine atom or an alkoxy group. R ₂₃ represents a substituent, and n ₂ represents an integer of 1 to 5. R ₂₄ ,
R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ represent a hydrogen atom or a halogen atom.

The present inventors have also found that at least one of the photographic constituent layers contains at least one compound represented by the following general formula [BI], and / or the above general formula [M-
In I], it was found that the object of the present invention can be achieved more effectively when R ₂₁ is an arylthio group.

General formula [B-I]

[0016]

[Chemical 6]

In the formula, R ₃₁ and R ₃₂ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₃₃ , R ₃₄ and R ₃₅ represent a substituent. R
₃₁ and R ₃₂ , R ₃₃ and R ₃₄ , R ₃₄ and R ₃₅ can form a ring, respectively.

The present invention will be described in more detail below. In the general formula [I], examples of the alkyl group represented by R ₁₁ and R ₁₂ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and an n-butyl group.
Hexyl group, cyclohexyl group, n-octyl group, n-
Examples thereof include dodecyl group, and these alkyl groups may be further substituted with the following substituents.

(Examples of Substituents) Alkenyl group: eg, vinyl group, allyl group, etc. Alkynyl group: eg, propargyl group, etc. Aryl group: eg, phenyl group, naphthyl group, etc. Heterocyclic group: eg, pyridyl group, thiazolyl group, oxazolyl group, Imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.

Halogen atom: Fluorine atom, chlorine atom, bromine atom, iodine atom Alkoxy group: For example, methoxy group, ethoxy group, propyloxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group. , N-octyloxy group, n-dodecyloxy group, etc. Aryloxy group: For example, phenoxy group, naphthyloxy group, etc. Alkoxycarbonyl group: For example, methyloxycarbonyl group, ethyloxycarbonyl group, n-butyloxycarbonyl group, n-octyl group Oxycarbonyl group, n-dodecyloxycarbonyl group, etc. Aryloxycarbonyl group: For example, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc. Sulfonamide group: For example, methylsulfonylamino group,
Ethylsulfonylamino group, n-butylsulfonylamino group, n-hexylsulfonylamino group, cyclohexylsulfonylamino group, n-octylsulfonylamino group, n-dodecylsulfonylamino group, phenylsulfonylamino group, etc.

Sulfamoyl group: For example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, n-butylaminosulfonyl group, n-hexylaminosulfonyl group, cyclohexylaminosulfonyl group, n-octylaminosulfonyl group, n-dodecyl group. Aminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc. Ureido group: For example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group,
n-octylureido group, n-dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.

Acyl group: for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, onyl group, n-pentylcarbonyl group, cyclohexylcarbonyl group, n-
Octylcarbonyl group, 2-ethylhexylcarbonyl group, n-dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc. Carbamoyl group: For example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group , N-pentylaminocarbonyl group, cyclohexylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, n-dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2
-Pyridylaminocarbonyl group etc. Amido group: For example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, n-pentylcarbonylamino group, cyclohexylcarbonylamino group, n-octylcarbonylamino group, 2- Ethylhexylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.

Sulfonyl group: For example, methylsulfonyl group, ethylsulfonyl group, n-butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc. Group: For example, amino group, ethylamino group, dimethylamino group, n-butylamino group, cyclopentylamino group, 2-ethylhexylamino group, n-dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc. Cyano group, nitro group, carboxy group, hydroxy group, sulfo group, etc.

Examples of the alkenyl group represented by R ₁₁ and R ₁₂ include a vinyl group and an allyl group, and these alkenyl groups are alkyl groups represented by R ₁₁ and R ₁₂ .
And a substituent similar to those exemplified as the substituent of the alkyl group.

Examples of the alkynyl group represented by R ₁₁ and R ₁₂ include a propargyl group and the like. These alkynyl groups are the alkyl groups represented by R ₁₁ and R ₁₂ , and the substituents exemplified as the substituents of the alkyl group. It can be substituted by a group similar to the group.

In the general formula [I], the alkyl group represented by R ₁₁ and R ₁₂ is preferably a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms and 1 to 4 carbon atoms. Is particularly preferred. At least one of R ₁₁ and R ₁₂ is preferably a substituent selected from a sulfoalkyl group or a carboxyalkyl group. Also, R
_{As the} substituted alkyl group represented by ₁₂ , JP-A-5-9397
Alkyl groups containing a substituent capable of dissociating in an alkaline solution as described in No. 8 and No. 6-82948 are also preferably used in the present invention.

R ₁₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. An ethyl group is particularly preferable.

The benzoxazole nucleus represented by Z ₁₁ may have a substituent, and specific examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), and a carbon number of 6 The following alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, etc.), aryl groups (eg, phenyl group, etc.),
An alkoxy group having 4 or less carbon atoms (eg, methoxy group, ethoxy group, butoxy group), an aryloxy group (eg, phenoxy group), an acyl group having 6 or less carbon atoms (eg, acetyl group, propionyl group, benzoyl group), Examples thereof include alkoxycarbonyl groups having 8 or less carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group), hydroxy group, cyano group, trifluoromethyl group, and the like.

The benzothiazole nucleus or benzoselenazole nucleus represented by Z ₁₂ may have a substituent, and specific examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.). ), An alkyl group having 6 or less carbon atoms (eg, methyl group, ethyl group, propyl group,
Butyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group), alkoxy group having 4 or less carbon atoms (eg, methoxy group, ethoxy group, butoxy group), aryloxy group (eg, phenoxy group), carbon number 6 The following acyl group (eg, acetyl group, propionyl group, benzoyl group, etc.), alkoxycarbonyl group having 8 or less carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), hydroxy group, etc. Can be mentioned.

(X) n ₁ is included in the formula to indicate the presence or absence of a cation or anion when required to neutralize the ionic charge of the dye. Therefore, n ₁ can take an appropriate value of 0 or more as necessary. Typical cations are inorganic or organic ammonium ions, alkali metal ions, alkaline earth metal ions, while anions include, for example, halogen anions, substituted aryl sulfonate ions, alkyl sulfate ions, thiocyanate ions, Examples thereof include perchlorate ion and tetrafluoroborate ion.

The sensitizing dyes used in the present invention are described in "Heterocyclic Compounds-Cyanine Dyes an" by FM Hamer, "Heterocyclic Compounds-Cyanine Dyes and Relayed Compounds".
d Related Compounds ”, Chapter 4, Chapter 5, Chapter 6, pages 86-119, John Willey and Sons
ey and Sons) (1964), DM Starmer (DMStur)
mer), Heterocyclic Compounds-Special Topics in Hete
rocyclic Chemistry ”, Chapter 8, pp. 482-515, published by John Wiley and Sons (1977), and the like.

Specific examples of the sensitizing dye represented by the general formula [I] used in the present invention are shown below, but the invention is not limited thereto.

General formula [I]

[0034]

[Chemical 7]

[0035]

Embedded image

[0036]

[Chemical 9]

[0037]

[Chemical 10]

The above sensitizing dye can also be used in combination with other sensitizing dyes or supersensitizers. Other cyanine dyes are preferable as the sensitizing dye to be combined with the sensitizing dye according to the present invention.

Examples of supersensitizers to be combined with the sensitizing dyes of the present invention include, for example, JP-A-3-219233 and Japanese Patent Application No.
The styryl compounds and hemicyanine compounds described in -225511 and the like are preferably used.

The addition amount of the sensitizing dye is preferably in the range of 2 × 10 ⁻⁶ to 1 × 10 ⁻² mol, and more preferably 5 × 1 per mol of silver halide.
The range of 0 ^{-6 to} 5 x 10 ^-3 mol is more preferable.

A method well known in the art can be used to add the sensitizing dye to the silver halide emulsion.
For example, these sensitizing dyes can be directly dispersed in an emulsion, or they can be dissolved in a water-soluble solvent such as pyridine, ethanol, methyl cellosolve, fluorinated alcohol or a mixture thereof, and the emulsion in the form of these solutions. Can also be added to.

As the sensitizing dye, as described in US Pat. No. 3,469,987, the dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion. As described in JP-B-46-24185 and the like, a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and the dispersion is added to an emulsion can also be used.

When the sensitizing dye represented by the general formula [I] used in the present invention is added to the emulsion, it is optional during the production process from the formation of silver halide grains to immediately before the coating on the support. Can be added at the time of, and may be added in plural times. The order of addition of the stabilizer and the antifoggant is not limited, but it is preferably added at the time of grain formation or chemical ripening, that is, at the step before the preparation of the coating solution.

The sensitizing dye represented by the general formula [I] according to the present invention is not particularly limited as long as it is a photographic constituent layer, but it is preferable to introduce it into the green-sensitive silver halide emulsion layer. When having a plurality of green-sensitive silver halide emulsion layers,
The layer to be introduced may be only one of the layers or a plurality of layers. It may also be incorporated in the green-sensitive layer and other constituent layers and / or other color-sensitive layers.

The photographic constituent layer in the present invention means a hydrophilic colloid layer on a support. These hydrophilic colloid layers are roughly classified into a light-sensitive silver halide emulsion layer and a non-light-sensitive silver halide emulsion layer. The former has a silver halide emulsion layer spectrally sensitized to light in a specific wavelength range, and usually they are a blue-sensitive silver halide emulsion layer (hereinafter referred to as "blue-sensitive layer" if necessary) and a green-sensitive halogen. A silver halide emulsion layer (hereinafter referred to as "green sensitive layer" if necessary) and a red sensitive silver halide emulsion layer (hereinafter referred to as "red sensitive layer" if necessary). The latter includes a layer for protecting the silver halide emulsion layer, a filter layer for blocking unnecessary light (for example, blue light), an intermediate layer or an antihalation layer. Further, each photosensitive silver halide emulsion layer has a single emulsion layer constitution or a constitution of two or more layers depending on the purpose.

Next, the magenta coupler represented by the general formula [MI] will be described. R ₂₁ represents a hydrogen atom or a substituent, and examples of the substituent include an arylthio group (for example, a phenylthio group), a carboxypropylthio group, an octylthio group, and the like, and an arylthio group such as a phenylthio group from the viewpoint of color development. Is preferred. It is more preferable to have an acylamino group at the ortho position with respect to the position of the sulfur atom in the phenylthio group in terms of color development.

R ₂₂ represents a chlorine atom or an alkoxy group, and examples of the alkoxy group include methoxy group, ethoxy group, isopropyloxy group, t-butyloxy group, n-
A hexyloxy group and the like can be mentioned.

R ₂₃ represents a substituent and any monovalent group may be used, and when n ₂ is 2 or more, R ₂₃ is 2
It may represent more than one kind of group.

Examples of the substituent of R ₂₃ include an alkyl group such as a methyl group, an isopropyl group and a trifluoromethyl group,
Examples thereof include alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, halogen atoms such as fluorine atom, chlorine atom and bromine atom, nitro group, amino group, dimethylamino group and alkylamino group.

It is preferable that at least one R ₂₃ is substituted in the ortho position with respect to the position of the NHCO group in order to reduce the concentration dependence of the spectral absorption wavelength of the color forming dye.

N ₂ represents an arbitrary integer of 1 to 5.

R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ and R _{28 each} represent a hydrogen atom or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, and the spectral absorption wavelength of the color-forming dye becomes a desired wavelength. And that the raw materials are available at a relatively low price,
₂₄ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ are preferably chlorine atoms.

Typical examples of the magenta coupler represented by the general formula [MI] are shown below, but the invention is not limited thereto.

[0054]

[Chemical 11]

[0055]

[Chemical 12]

[0056]

[Chemical 13]

[0057]

Embedded image

[0058]

[Chemical 15]

[0059]

Embedded image

These couplers can be used together with magenta couplers other than the present invention, and usually 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-2 to 8 mol per mol of silver halide.
It can be used in a range of × 10 ^-1 mol.

The coupler represented by the general formula [MI] according to the present invention can be introduced into the light-sensitive material by various known dispersion methods. For example, tricresyl phosphate, a high boiling point organic solvent having a boiling point of 175 ° C. or higher such as dibutyl phthalate, a low boiling point solvent such as butyl acetate or butyl propionate, or the couplers are dissolved in a mixed solution thereof as necessary. After that, it can be mixed with an aqueous gelatin solution containing a surfactant, and then emulsified with a high-speed rotary mixer or a colloid mill, and then added to the silver halide emulsion.

The layer in which the coupler represented by the general formula [MI] according to the present invention is introduced may be the same as or different from the layer containing the emulsion spectrally sensitized by the sensitizing dye according to the present invention. It is preferable to add them to the same layer.

Next, the compound represented by the general formula [BI] will be described. In the general formula [BI], examples of the alkyl group represented by R ₃₁ and R ₃₂ include a methyl group, an ethyl group, and n.
-Propyl group, isopropyl group, tert-butyl group,
n-pentyl group, cyclopentyl group, n-hexyl group,
Examples thereof include a cyclohexyl group, n-octyl group, n-dodecyl group, etc., examples of the alkenyl group include vinyl group, allyl group, etc., examples of the alkynyl group include propargyl group, etc., and examples of the aryl group include phenyl group. Examples of the heterocyclic group include pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group. , Pyrazolyl group, tetrazolyl group and the like.

The substituents represented by R ₃₃ , R ₃₄ and R ₃₅ include an alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n -Hexyl group, cyclohexyl group, n-octyl group, n-dodecyl group, etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg propargyl group etc.), aryl group (eg phenyl group, naphthyl group etc.) ), A heterocyclic group (for example, a pyridyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group,
Furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc., halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (For example, a methoxy group,
Ethoxy group, propyloxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group,
Cyclohexyloxy group, n-octyloxy group, n-
Dodecyloxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), alkoxycarbonyl group (eg methyloxycarbonyl group, ethyloxycarbonyl group, n-butyloxycarbonyl group, n-octyloxycarbonyl group, n -Dodecyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group, naphthyloxycarbonyl group etc.), sulfonamide group (eg methylsulfonylamino group, ethylsulfonylamino group, n-butylsulfonylamino group, n- Hexylsulfonylamino group, cyclohexylsulfonylamino group, n-octylsulfonylamino group, n-dodecylsulfonylamino group, phenylsulfonylamino group, etc., sulfamoyl group (for example, aminosulfonyl group) Methylaminosulfonyl group, dimethylaminosulfonyl group, n-butylaminosulfonyl group, n-hexylaminosulfonyl group, cyclohexylaminosulfonyl group, n-octylaminosulfonyl group, n-dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylamino Sulfonyl group, 2-pyridylaminosulfonyl group, etc., ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, n-octylureido group, n-dodecylureido group, phenylureido group, naphthylureido group) , 2-pyridylaminoureido group, etc., acyl group (eg, acetyl group, ethylcarbonyl group, propylcarbonyl group, n-pentylcarbonyl group, cyclohexylcarbonyl group, n-octyl group) Rubonyl group, 2-ethylhexylcarbonyl group, n-dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc., carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group) Group, n-pentylaminocarbonyl group, cyclohexylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, n-
Dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc., amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, n-pentyl group) Carbonylamino group, cyclohexylcarbonylamino group, n-octylcarbonylamino group, 2-ethylhexylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc., sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group) Group, n-butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthyls Honyl group, 2-pyridylsulfonyl group, etc., amino group (for example, amino group, ethylamino group, dimethylamino group, n-butylamino group, cyclopentylamino group, 2-ethylhexylamino group, n-dodecylamino group, anilino group) , Naphthylamino group, 2-
Pyridylamino group), cyano group, nitro group, carboxy group, hydroxy group, sulfo group, hydrogen atom and the like. Further, these groups can be substituted with an alkyl group represented by R ₃₁ or R ₃₂ or a group similar to the groups shown as examples of the substituent of the alkyl group in the above.

R ₃₁ and R ₃₂ , R ₃₃ and R ₃₄ , R ₃₄
And R ₃₅ each can form a ring,
Examples of the ring formed by ₃₁ and R ₃₂ include a piperidine ring, a pyrrolidine ring, a morpholine ring, a pyrrole ring, a piperazine ring, and a thiomorpholine ring. Examples of the ring formed by R ₃₃ and R ₃₄ or R ₃₄ and R ₃₅ include a benzene ring, a thiophene ring, a furan ring, a pyrrole ring and the like.

Specific examples of the compound represented by the general formula [BI] are shown below, but the invention is not limited thereto.

[0067]

[Chemical 17]

The compound represented by the general formula [BI] according to the present invention is added in the range of 1 mol% to 500 mol% with respect to the coupler represented by the general formula [MI]. A more preferable addition amount is 5 mol% or more and 300 mol% or more. The layers to be added may be the same as or different from those in which the coupler represented by the general formula [MI] is introduced, but it is preferable to add them in the same layer. The addition to the silver halide emulsion can be carried out at the same time as the coupler or at a different timing.

The compound represented by the general formula [BI] has the general formula
It can be introduced into the light-sensitive material by various known dispersion methods similar to those used for introducing the coupler represented by [MI]. The compound represented by the general formula [BI] can be dispersed by dissolving it in the same organic solvent as the coupler, or separately from the coupler, and can be dissolved in a suitable solvent. It is preferable to dissolve and disperse in the same solvent as the coupler represented by [MI]. Alternatively, without using an organic solvent, it can be directly dispersed in a gelatin aqueous solution containing a surfactant simultaneously with the coupler or separately from the coupler by a high-speed rotary mixer or the like.

The preferred silver halide contained in the color photographic light-sensitive material of the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide, preferably 2 mol% or more and 25 mol% or less iodide. It is silver iodobromide or silver iodochlorobromide containing silver.

The above silver halides have regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular shapes such as spheres and plates, and those having crystal defects such as twin planes. Or, it is used as particles of their composite system.

The grain size of silver halide is not particularly limited,
Either a polydisperse emulsion or a monodisperse emulsion may be used, but a monodisperse emulsion is preferred.

The silver halide emulsion which can be used in the present invention is
For example, Research Disclosure No.17643 (1978
22-23, and No. 18716 (1989), 648, 648, "The Physics and Chemistry of Photography" by Graph Candet, published by Paul Montel.
(P.Glafkides, Chemicet Phisique Photographique, Pa
ul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion
It can be prepared using the method described in Chemistry, Focal Press, 1966) and the like.

The silver halide grains preferably used in the present invention are tabular grains having an aspect ratio of 2 or more, more preferably having an aspect ratio of 3 or more and less than 20, and an aspect ratio of 5 or more and less than 10. More preferred are: It is preferable that these tabular grains contain 50% or more of the grain projected area. Such tabular grains are U.S. Pat.Nos. 4,434,226, 4,414,310, and 4,439,
It can be prepared by the method described in No. 520 or the like.

The silver halide emulsion used in the present invention is Research Disclosure (referred to as RD) 308.
Those described in 119 can be used.

The description is given below.

[Item] [Page of RD308119] Iodine composition 993 IA Item Manufacturing method 〃 and 994 E Item Crystal habit Normal crystal 〃 〃 Twin crystal 〃 〃 Epitaxial 〃 Halogen composition Uniform 993 IB Item Non-uniform 〃 〃 Halogen conversion 994 IC item Halogen substitution 〃 Metal 〃 ID item Monodisperse 995 IF item Solvent addition 〃 Latent image formation surface 995 IG item Inner surface 〃 Application sensitive material Negative 995 IH item Positive (including internal fog particles) 〃 Mixing emulsions 〃 Item IJ Desalting 〃 Item II-A

In the present invention, the silver halide emulsion is used after physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RD176
43, 18716 and 308119.

The description places are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649

Known photographic additives that can be used in the present invention are also described in the above RD. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 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 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matting agent 1007 XVI Developer (included in photosensitive material) 1011 XXB

Various couplers can be used in the present invention, specific examples of which are described in RD above. The relevant locations are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Yellow coupler 1001 VII-D item VIIC-G item Cyan coupler 1001 VII-D item VIIC-G item Colored coupler 1002 VII-G item VIIG item DIR coupler 1001 VII-F item VIIF item BAR coupler 1002 VII-F item Other useful residue releasing coupler 1001 VII-F item Alkali-soluble coupler 1001 VII-E item

The additive used is X of RD308119.
It can be added by the dispersion method described in IV.

In the present invention, RD17643, page 28, RD18716, pages 647-8, and RD308.
The supports described in XIX of 119 can be used.

The light-sensitive material of the present invention includes the above-mentioned RD3081.
An auxiliary layer such as a filter layer or an intermediate layer described in the section 19VII-K can be provided.

The light-sensitive material of the present invention is the same as the above-mentioned RD30811.
Various layers and configurations such as the forward layer, the reverse layer, and the unit configuration described in Section 9VII-K can be adopted.

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, and color positive films.

The light-sensitive material of the present invention is the above-mentioned RD17643.
28-29, RD18716, page 615 and RD3.
By the usual method described in XIX of 08119,
It can be developed.

[0091]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Sample No. 101) Silver iodide having an average grain size of 0.4 μm
Optimum gold-sulfur sensitization was performed on a silver iodobromide emulsion having an average silver iodide content of 8 mol% having a core of 15 mol%, and sensitizing dye I-2 was added to silver 1
7.5 × 10 ^-5 mol was added per mol to spectrally sensitize to green. Then, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added for stabilization.

Further, the comparative magenta coupler MR-1 was mixed with ethyl acetate in an amount of 2.2 mol per mol of silver halide.
Dissolve in tricresyl phosphate (TCP), emulsify and disperse it in an aqueous solution containing gelatin, and add common photographic additives such as extenders and hardeners to prepare coating solutions, which are subbed. A light-sensitive material sample No. 101 was prepared by coating on a cellulose acetate support by a conventional method and drying.

(Preparation of Sample No. 102 to No. 108) Sample No. 101
Sample No. 1 except that the sensitizing dye I-2 or coupler MR-1 in Example 1 is replaced with the dye or coupler shown in Table 1 in equimolar amounts, respectively.
Created in exactly the same way as 01.

[0095]

Embedded image

Each sample was subjected to wedge exposure according to a conventional method and processed in the following processing steps to evaluate fog and sensitivity. The sensitivity was shown as a relative value with the sensitivity of Sample No. 101 set to 100. The results are shown in Table 1.

[0097]

The composition of the processing liquid used in each processing step is as follows.

(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 2.00 g Anhydrous potassium carbonate 37.50 g Sodium bromide 1.30 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.50 g Potassium hydroxide 1.00 g Water is added to make 1 liter and pH is adjusted to 10.1.

(Bleach) Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Water was added to make 1 liter, and ammonia water was added. Use pH 6.
Adjust to 0.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, 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.

Each sample was tested at a temperature of 55 ° C. and a relative humidity of 6
After storage at 0% for 3 days, wedge exposure with green light was similarly performed, development processing was performed, and the results of evaluation of the storability of the light-sensitive material over time from changes in relative sensitivity are also shown.

Table 1 Sample No. Coupler Sensitizing dye Fog Relative sensitivity Storage stability * 101 (Comparison) MR-1 I-2 0.09 100 27 102 (Comparison) MR-2 I-2 0.11 112 23 103 (Comparison) MR-3 I-2 0.10 108 21 104 (Invention) M-27 I-2 0.05 125 10 105 (Invention) M-1 I-2 0.04 245 13 106 (Invention) M-3 I-2 0.05 249 11 107 (Invention) M-8 I-2 0.06 244 12 108 (Invention) M-15 I-2 0.07 247 14 109 (Invention) M-18 I-2 0.06 232 13 110 (Comparison) M-27 SR-1 0.09 54 35

* The relative value of the sensitivity variation of the sample forcibly deteriorated by being stored at a temperature of 55 ° C. and a relative humidity of 60% for 3 days, based on the green light sensitivity immediately after preparation of the coated sample, is shown. The smaller the value, the better the storage stability over time.

As is clear from Table 1, the samples of the present invention have low fog, high sensitivity and good storability over time.

Example 2 (Preparation of Silver Halide Emulsion) An octahedral silver iodobromide emulsion having a (111) face was mainly used according to the method described in JP-A-60-138538, and a tabular twin emulsion. Japanese Patent Laid-Open No. 3-94248
The emulsions A to F as shown in Table 2 were prepared according to the method described in Japanese Patent Publication No.

Emulsion name Average grain size Grain shape Aspect ratio Average silver iodide content (μm) (mol%) Emulsion A 0.30 octahedron 1.0 4.0 Emulsion B 0.42 octahedron 1.0 6. 0 Emulsion C 0.55 Flat plate 2.0 6.0 Emulsion D 0.85 Flat plate 2.2 6.0 Emulsion E 0.95 Flat plate 2.0 6.0 Emulsion F 0.85 Flat plate 5.2 6.0

(Preparation of Sample Nos. 201 to 215) On the triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare Sample No. 1 of the multilayer color photographic light-sensitive material. 201 ~ No.215 was created.

[0110] The amount coated amount (Composition of photosensitive layer) was expressed in terms of metallic silver for silver halide and colloidal silver in the unit of g / m ^2, also couplers, for additives and gelatin g / m ² The amount added in units is shown as the number of moles per mole of silver halide in the same layer for the sensitizing dye.

First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60

Second layer: intermediate layer Compound (SC-1) 0.14 High boiling point solvent (OIL-4) 0.17 Gelatin 0.80

Third Layer: Low Sensitivity Red Sensitive Layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ⁻⁴ Sensitizing dye (SD-2 ) 1.4 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.4 × 10 ⁻⁵ Sensitizing dye (SD-4) 0.7 × 10 ⁻⁴ Cyan coupler (C-2) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09

Fourth Layer: Medium Sensitivity Red Sensitive Layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-1) 1.7 × 10 ⁻⁴ Sensitizing dye (SD-2) ) 0.86 × 10 ^-4 sensitizing dye (SD-3) 1.15 × 10 ^-5 sensitizing dye (SD-4) 0.86 × 10 ^-4 cyan coupler (C-2) 0.33 color cyan coupler (CC-1) 0.013 DIR compound (D-1) 0.02 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79

Fifth layer: High-sensitivity red-sensitive layer Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-1) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.2 × 10 ⁻⁵ Cyan coupler (C-1) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79

Sixth layer: intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-4) 0.11 Gelatin 0.80

Seventh Layer: Low Sensitivity Green Sensitive Layer Silver Iodobromide Emulsion A 0.12 Silver Iodobromide Emulsion B 0.38 Sensitizing Dye (SD-4) 4.6 × 10 ⁻⁵ Sensitizing Dye (SD-5) ) 4.1 × 10 ^-4 Magenta coupler (M-2) 0.14 Magenta coupler (M-3) 0.14 Colored magenta coupler (CM-1) 0.03 Colored magenta coupler (CM-2) 0.03 High boiling point Solvent (OIL-2) 0.34 Gelatin 0.70

Eighth layer: Intermediate layer Gelatin 0.41

Layer 9: Medium-Sensitivity Green Sensitive Layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-6) 1.2 × 10 ⁻⁴ Sensitizing dye (SD-7) ) 1.2 × 10 ^-4 Sensitizing dye (SD-8) 1.2 × 10 ^-4 Magenta coupler (M-2) 0.04 Magenta coupler (M-3) 0.04 Colored magenta coupler (CM-1) 0.008 Colored magenta coupler (CM-2) 0.009 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (OIL-2) 0.12 Gelatin 0.50

Layer 10: High-sensitivity green-sensitive layer Silver iodobromide emulsion (described in Table 2) 0.95 Sensitizing dye (SD-8) 16.2 × 10 ⁻⁵ Sensitizing dye (described in Table 2) 5.1 × 10 ^{− 5} Magenta coupler (described in Table 2) 0.09 Colored magenta coupler (CM-1) 0.005 Colored magenta coupler (CM-2) 0.006 Compound of general formula [BI] (described in Table 2) 0.027 High boiling point Solvent (OIL-2) 0.11 Gelatin 0.79

Eleventh layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-4) 0.19 Gelatin 1.10

Twelfth layer: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D- 5) 0.02 High boiling point solvent (OIL-4) 0.42 Gelatin 1.40

Thirteenth layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10 ⁻⁵ Sensitizing dye (SD-11 ) 3.1 × 10 ^-5 Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-4) 0.05 Gelatin 0.79

Fourteenth Layer: First Protective Layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 ultraviolet absorber (UV-1) 0.065 high boiling solvent ( OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65

Fifteenth 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, coating aid SU-1, dispersion aid SU-2, viscosity modifier, hardeners H-1, H-2, stabilizer ST-
1, antifoggant AF-1, AF-2, AF-3, average molecular weight: 10,00
Two kinds of AF-4 with 0 and average molecular weight: 1,100,000, and preservative
DI-1 was added.

[0127]

[Chemical 19]

[0128]

Embedded image

[0129]

[Chemical 21]

[0130]

[Chemical formula 22]

[0131]

[Chemical formula 23]

[0132]

[Chemical formula 24]

[0133]

[Chemical 25]

[0134]

[Chemical formula 26]

[0135]

[Chemical 27]

[0136]

[Chemical 28]

For each sample, exposure, development, fog,
The relative sensitivity and storability with time were evaluated in the same manner as in Example 1. However, the sensitivity of Sample No. 201 was set to 100. The results are shown in Table 2. Table 2 Sample No. Coupler Sensitizing dye Compound Emulsion Fog Relative sensitivity BI storage stability 201 (Comparison) MR-1 I-16-D 0.10 100 22 202 (Comparison) M-17 SR-1-D 0.11 84 35 203 ( (Comparison) M-17 SR-2-D 0.11 60 43 204 (Invention) M-17 I-16-D 0.06 239 12 205 (Invention) M-17 I-1-D 0.05 235 14 206 (Invention) M-3 I-1-D 0.07 241 16 207 (Invention) M-3 I-16-D 0.07 243 15 208 (Invention) M-3 I-1 B-2 D 0.03 248 10 209 (Invention) M-3 I-1 B-5 D 0.03 252 9 210 (Invention) M-3 I-2 B-5 F 0.02 274 7 211 (Invention) M-3 I-5 B-5 F 0.03 270 8 212 (Invention) M-3 I-8 B-5 F 0.04 266 10 213 (Invention) M-3 I-12 B-5 F 0.03 273 8 214 (Invention) M-3 I-16 B-5 F 0.02 269 7 215 (Invention) M-3 I-17 B-5 F 0.03 265 11 216 (Invention) M-3 I-20 B-5 F 0.03 270 9

As is clear from Table 2, the combination of the coupler of the present invention and the sensitizing dye shows low fog, high sensitivity and good storage stability over time. Further, when comparing the samples No.204 ~ No.207 of the present invention and No.208 ~ No.216, the sample No.208 ~ No.216 using the compound BI.
Shows that fog and storability with time are further improved, which is a preferable embodiment of the present invention.

[0139]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material having low fog, high sensitivity and excellent storage stability of the manufactured light-sensitive material.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one photographic constituent layer on a support, wherein at least one photographic constituent layer contains a sensitizing dye represented by the following general formula [I]: At least one and the following general formula [MI]
A silver halide color photographic light-sensitive material containing at least one coupler represented by: General formula [I] [Wherein, R ₁₁ and R ₁₂ represent a substituent selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group, and R ₁₃ represents a hydrogen atom,
It represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Z ₁₁ represents an atomic group necessary for forming a substituted or unsubstituted benzoxazole nucleus,
₁₂ represents an atomic group necessary for forming either a substituted or unsubstituted benzothiazole nucleus or a substituted or unsubstituted benzoselenazole nucleus. X represents a charge-balancing counterion, and n ₁ represents a numerical value for controlling the charge of the whole molecule. ] General formula [MI] [In the formula, R ₂₁ represents a hydrogen atom or a substituent, and R ₂₂ represents a chlorine atom or an alkoxy group. R ₂₃ represents a substituent, and n ₂ represents an integer of 1 to 5. R ₂₄ , R ₂₅ , R ₂₆ ,
R ₂₇ and R ₂₈ represent a hydrogen atom or a halogen atom. ] 2. A silver halide color photographic light-sensitive material according to claim 1, wherein at least one of the photographic constituent layers contains at least one compound represented by the following general formula [BI]. General formula [BI] [In the formula, R ₃₁ and R ₃₂ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₃₃ , R ₃₄ and R ₃₅ represent a substituent. R ₃₁ and R ₃₂ ,
R ₃₃ and R ₃₄ , and R ₃₄ and R ₃₅ can form a ring, respectively. ] 3. The silver halide color photographic light-sensitive material according to claim 1, wherein R ₂₁ in the general formula [MI] is an arylthio group.