JPH0652410B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material which exhibits little performance fluctuation during product storage and is excellent in stability. When the present invention is applied to a silver halide photographic light-sensitive material for color photographic paper, particularly preferable effects can be obtained.

(Prior Art) Various methine dyes such as cyanine dyes and merocyanine dyes are used alone or in admixture of these dyes in order to impart spectral sensitivity to silver halide photographic emulsions and reproduce natural colors. Used in combination with a sensitizer.

Useful cyanine dyes are classified into monomethine dyes, trimethine dyes (carbocyanine dyes), pentamethine dyes (dicarbocyanine dyes), etc. according to the length of their methine chains, and they are each blue according to their spectral absorption wavelength. It is used as a spectral sensitizing dye for the sensitive layer, green sensitive layer and red sensitive layer.

Further, among these dyes, it is known to use, for example, a mixture of a monomethine dye and a carbocyanine dye (for example, JP-B-48-1762 and JP-A-50-288).
No. 26, No. 51-14313, No. 58-153926.
issue).

On the other hand, in a silver halide photographic light-sensitive material for color photographic paper, a silver halide emulsion constituting a light-sensitive emulsion layer is generally a halogen containing substantially no iodine such as silver chloride, silver bromide, silver chlorobromide. Silver halide is preferably used. One of the reasons for this is that a hard gradation silver halide emulsion capable of forming an image with high contrast can be obtained with the smallest possible amount of silver. This is because an excellent silver halide emulsion can be obtained. It is also known that a silver halide emulsion containing substantially no iodide has a high desilvering rate even in the bleach-fixing process after the color developing process and is preferable for color photographic paper.

However, even with a silver chlorobromide emulsion having such good performance, fluctuations in performance during storage of the product, particularly increase in fog during long-term storage, are likely to occur, and in particular, the silver chloride content was increased in order to accelerate the developing speed. This tendency is remarkable in the silver chlorobromide emulsion, which is a problem in supplying a product with stable performance, and solving it is an important issue.

Several techniques have been conventionally proposed as means for improving such storability. For example, it is well known that the preservation property is improved by adding azoles, mercapto compounds, azaindenes and the like used as so-called stabilizers, and a specific example thereof is "Stabili" by E.J.A. Seesion of Photograph Itik Silver Halide Emulations "(Stabilization
of Photographic Silver Halide Emulsions) (Foral Press, 1974).

(Problems to be solved by the invention) However, as a result of the research conducted by the present inventors, the azoles, mercapto compounds, and azaindenes used as the above stabilizers are generally compounds strongly adsorbed to silver halide grains. While it has a remarkable effect on stabilizing performance and preventing fog, when the amount used is increased, adsorption of additives such as the spectral sensitizing dyes described above to silver halide is hindered and desensitization and softening are performed. It has been found that this is a case where it also has some side effects such as causing it and inhibiting desilvering during bleach-fixing processing. In particular, when used for the purpose of preventing an increase in fog during storage of a silver chlorobromide-based emulsion, such restrictions often cannot be effective means.

Therefore, the object of the present invention is to improve performance during storage of products,
In particular, it is an object of the present invention to provide a silver halide color photographic light-sensitive material which is suppressed in the increase of fog and has excellent stability. At the same time, another object of the present invention is to provide a silver halide color photographic light-sensitive material having a high color developing rate, excellent processability, and a high desilvering rate in the bleach-fixing process after the color developing process.

(Means for Solving the Problems) As a result of the research conducted by the present inventors to achieve the above object, as a result, a silver chlorobromide emulsion (silver chloride content of 80 mol%) containing substantially no iodine was found. In a color photographic light-sensitive material having at least one photosensitive emulsion layer containing the following) coated on a support, at least one of the photosensitive emulsion layers has the following general formulas (IA) and (IB). Or by using at least one of the compounds represented by (IC) and at least one of the compounds represented by the following general formula (II-A) or (II-B). At least one compound represented by the following general formula (III) and / or at least one compound represented by the following general formula (IV), which contains a spectrally sensitized silver halide emulsion Halogen characterized by being dura mater It has been found that the object of the present invention can be effectively achieved by using a silver halide color photographic light-sensitive material.

General formula [IA] [IB] [IC] General formula (II-1) General formula (II-B) General formula (III) General formula (IV) Conventionally, many studies have been carried out on a technique of using a cyanine dye having a different methine chain, but most of them are related to a supersensitizing effect by using a spectral sensitizing dye in combination. Examples of these are Japanese Patent Publication No. 48-1762 and Japanese Patent Laid-Open No. 50-2882.
No. 6 and No. 51-14313 can be named. It goes without saying that these techniques could not achieve the object of the present invention to suppress the fog that occurs during storage of a light-sensitive material using a silver chlorobromide emulsion containing substantially no iodine. Further, it is described in JP-A-58-153926 that the storage stability is improved by using a combination of a specific combination of spectral sensitizing dyes, and the technique also provides the above object of the present invention. Has little effect on.

Further, conventionally, it has been known that the preservability is good when a compound represented by the general formula (III) and / or (IV) is used as a hardener for a gelatin film. For example, it is described in Japanese Examined Patent Publication No. 47-6151. However, even with respect to the increase in fog during storage of a light-sensitive material using a silver chlorobromide emulsion containing substantially no iodide, such a technique cannot provide a sufficient effect. The effect of the present invention is represented by the general formula (IA, B, C).
A photosensitive emulsion layer containing a silver halide emulsion spectrally sensitized by using the compound represented by the formula (II-A, B) in combination with the compound represented by the formula (III) and / or It is a completely novel compound that is remarkably exhibited only when a film is hardened using the compound represented by (IV).

The sensitizing dyes represented by formulas [IA], [IB] and [IC] will be described in more detail.

W ₁ and W ₂ represent a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 6, for example, methyl group, ethyl group, propyl group, butyl group, etc.).

W ₁ is preferably an ethyl group or a propyl group,
W ₂ is preferably a hydrogen atom.

V ₁ , V ₂ , V ₃ , and V ₄ are hydrogen atom, halogen atom (for example, chlorine atom, bromine atom, etc.), alkyl group (preferably having 1 to 8 carbon atoms, for example, methyl group, ethyl group, Propyl group, butyl group, trifluoromethyl group, etc.), aryl group (eg, phenyl group, etc.), alkoxy group (preferably having 1 to 8 carbon atoms, eg,
Methoxy group, ethoxy group, propoxy group, etc.), amide group (preferably having 2 to 8 carbon atoms, for example, acetamide group, propionamide group, benzamide group, etc.),
It represents an alkoxycarbonyl group (preferably having 2 to 8 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc.) or a cyano group. V ₁ and V ₂ and V ₃ and V ₄ may be the same or different,
V ₁ , V ₂ and V ₃ may be a condensed benzene ring.

V ₅ and V ₆ may be the same or different, and said V ₁ ,
Among the groups described for V ₂ , V ₃ and V ₄ , those other than the aryl group and the condensed benzene ring are represented.

Two or more substituents represented by V _{1 to} V ₆ may be contained in the same molecule.

Next, preferred cases of V _{1 to} V ₆ will be described.

When Y represents an oxygen atom, V ₁ is preferably a phenyl group or a condensed benzene ring, and V ₂ is preferably a phenyl group, a condensed benzene ring, a chlorine atom or an alkoxy group.

When Y represents a sulfur atom, V ₂ is preferably a hydrogen atom, a halogen atom, an alkyl group, a phenyl group, an alkoxy group or an amide group.

V ₃ preferably represents a phenyl group or a chlorine atom, or is in the case of a fused benzene ring, V ₄ , V ₅ and V
₆ is preferably a trifluoromethyl group, a chlorine atom, an alkoxycarbonyl group, and a cyano group. Also,
In the general formula [I-C], it is also preferable that one of the two benzimidazolyl groups has one chlorine atom, or one has two chlorine atoms.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each a substituted or unsubstituted alkyl group (preferably having a carbon number of 8 or less, for example, a methyl group or an ethyl group). , Propyl group, butyl group, acetylethyl group, etc. It may be branched or cyclic, for example, isopropyl group, cyclohexyl group,
Etc.) or an aralkyl group (eg, benzyl group, phenethyl group, etc.). More preferably, it has 1 to 5 carbon atoms.
Or an aralkyl group having 7 to 10 carbon atoms.

These groups are 2 or 4 in the general formulas [IA], [IB] and [IC], but at least one of the groups present in the same molecule is a sulfone group or a carboxy group. It is preferably an alkyl group or an aralkyl group containing a group or a salt thereof or a hydroxyl group. Specific examples of such a substituent alkyl group and aralkyl group include sulfoethyl group, sulfopropyl group, sulfobutyl group, sulfopropoxyethyl group, 4-sulfophenylethyl group, 4-carboxyphenylethyl group, carboxymethyl group. , Carboxyethyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group and the like.

X ₁ , X ₂ and X ₃ represent counterions sufficient to neutralize the charge of the molecule. As the cation, for example, hydrogen ion,
Such as sodium ion, potassium ion, triethylammonium ion, and pyridinium ion,
Examples of the anion include chlorine ion, bromine ion and iodine ion.

L ₁ , m ₁ and n ₁ when the compound forms an inner salt
Is 0 and there is no counterion.

Among the compounds represented by the general formulas [IA], [IB] and [IC], the use of the compound represented by the general formula [IA] is preferable for achieving the object of the present invention, It is particularly preferable that Y in the general formula [IA] is an oxygen atom.

Next, the compounds represented by formulas [II-A] and [II-8] will be described in more detail.

Y ₁ and Y _{2 in the} general formula [II-A] each represent an atomic group sufficient to form a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus or a naphthothiazole nucleus,
Halogen atom such as fluorine, chlorine, bromine or iodine, or hydroxyl group, or methyl group,
Alkyl groups such as ethyl, propyl and butyl, alkoxy groups such as methoxy and ethoxy, aryl groups such as phenyl and hydroxyphenyl, and alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl. Alternatively, it may be substituted with a cyano group or a nitro group.

Specific examples of R ₁₀ and R _{11 in} the general formula [II-A] are the same as those described for R _{1 to} R ₉ .

At least one of R ₁₀ and R ₁₁ is preferably an sulfo group, a carboxyl group, a salt thereof, or a hydroxyl group-containing alkyl group or an aralkyl group.

Specific examples of the counter ion represented by X ₄ in the general formula [II-A] are the same as those listed in X _{1 to} X ₃ .

R ₁₂ and R _{13 in the} general formula [II-B] are an alkyl group, an alkenyl group or an aralkyl group which may be substituted with a hydroxyl group, a sulfone group or a carboxyl group directly or via a divalent group of an alkoxy group. Or an aryl group,
Specific examples thereof are the same as those described for R _{1 to} R ₉ .

Of these substituents, both R ₁₂ and R ₁₃ are preferably substituted or unsubstituted alkyl groups.

Specific examples of V ₇ and V ₈ each represent a group other than the condensed benzene ring among the groups described in the above V _{1 to} V ₄ .

V ₇ and V ₈ may be different from each other or may be the same, but a trifluoromethyl group, a chlorine atom, an alkoxycarbonyl group and a cyano group are preferable.

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

The sensitizing dyes represented by the general formulas [IA], [IB], and [IC] used in the present invention are known compounds. M. FM Hamer, “Heterocyclic Compou-Cyanine Soybean and Relayed Compounds”
nds-Cyanine Dyes and Related Compounds) ”, No. 5
Chapter, pp. 116-147, published by John Wiley and Sons (1964),
D. M. D. S. Sturmer, "Heterocyclic Compounds-Special Topicals in Heterocyclic Chemistry (Heterocyc
lic Compounds-Special Topics in Heterocyclic Chemi
stry) ", Chapter 8, Section 5, pp. 482-515, published by Jiyoung Wiley & Sons (1977), Japanese Examined Patent Publications 43-13823, 44-16589, 48-.
9966, 43-4936, and JP-A-52-82416.
It can be easily synthesized by referring to the method described in the above.

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

The sensitizing dyes represented by the general formulas [IA], [IB], and [IC] used in the present invention are from 1 × 10 ⁻⁶ mol to 5 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ mol, per mol of silver halide. It is contained in the silver halide emulsion layer in a proportion of x10 ^-5 mol to 2.5 x 10 ^-3 mol, particularly preferably 4 x 10 ^-5 mol to 1 x 10 ^-3 mol.

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

General formulas [II-A] and [II-B] used in the present invention
The compounds represented by the general formula [IA], [IB]
And the compound represented by [I-C] is preferably added in a ratio of 2 to 70 mol% with respect to the added amount (the amount when used alone, and the total amount when used in plural), and particularly preferably. It is preferable to add it at a ratio of 5 to 50 mol%.

In the present invention, for the silver chlorobromide emulsion containing substantially no iodide, the formulas [IA], [IB] and [IB] are used.
C] and at least one compound [II-A]
In order to perform spectral sensitization in combination with and at least one compound represented by [II-B], a commonly known method may be used. That is, the compound to be used is dissolved in an appropriate solvent (methanol, ethanol, ethyl acetate, etc.),
It is carried out by adding it to the silver halide emulsion as a solution having an appropriate concentration.

The above solution is added at any step during or after the production of the silver halide emulsion. For example, any step may be performed during the formation of silver halide grains, before and after chemical ripening, during chemical ripening, after chemical ripening, or after preparation of the coating solution, and the order of addition of the stabilizer and the antifoggant is not limited.

In order to fully exert the effects of the present invention, the general formula [I
-A], [IB] or [I-C] represented by compound (I) and general formula [II-A] or [II-B] represented by compound (II) Is preferably as follows. That is, it is preferable to add the compound II at the same time as or before the addition of the compound I, and it is particularly preferable to add the compound II as a mixed solution of the compound I and the compound II.

In the present invention, a compound exhibiting a supersensitizing effect can also be used in combination by combining a sensitizing dye in addition to compound I and compound II.

The hardener represented by the general formula (III) is represented by JP-B-47-61.
51, 47-33380, U.S. Pat.
743, JP-A-48-19220, 51-787.
No. 88, No. 52-60612, No. 52-128130
No. 52-130326 and No. 56-1043, and can be used among them.

The hardener represented by the general formula (IV) is disclosed in JP-B-58-3354
No. 2, JP-A No. 57-40244, and any of them can be used.

In the general formula (III), it is preferable that one of the substituents represented by R ₁₄ and R ₁₅ be a chlorine atom. R ₁₄ , R
_When the substituent represented by ₁₅ is -OM, M is preferably a sodium atom or a potassium atom.
When the substituent represented by R ₁₄ and R ₁₅ is an alkyl group or an alkoxy group, it is preferably a methyl group, an ethyl group, a butyl group, a methoxy group, an ethoxy group, a butoxy group or the like. Also -NH ₂ , -NHCH _{3 and the} like, and -NHCOR ₁₈ has -NHCOCH ₃
Etc. are used.

When the substituent represented by R ₁₉ and R ₂₀ in the general formula (IV) is an alkyl group or an alkoxy group, it is preferably a methyl group, an ethyl group, a butyl group, a methoxy group, an ethoxy group, a butoxy group or the like. When R ₁₉ and R ₂₀ are -OM, M is preferably a sodium atom or a potassium atom. L is _{-CH 2 -, - (CH 2} ) 2 -, Etc.

The compounds represented by these general formulas (III) and (IV) are
At least one of the compounds represented by formulas (IA), (IB), and (IC);
A), a layer containing a substantially iodine-free silver chlorobromide emulsion which has been spectrally sensitized by the combined use with at least one of the compounds represented by (II-B) or other It may be added concentratedly or dividedly to at least one or more layers among the layers. The addition amount may be 0.05 to 15% by weight of the gelatin amount of all layers regardless of the kind of the addition amount or the addition amount of gelatin. Preferably 0.2 to 10% by weight is added.

Specific examples of the compound represented by formula (III) or (IV) used in the present invention are shown below, but the present invention is not limited thereto.

The light-sensitive emulsion layer according to the present invention contains a magenta dye-forming coupler to form a green-sensitive emulsion layer, which is combined with a blue-sensitive emulsion layer containing a yellow dye-forming coupler and a red-sensitive emulsion layer containing a cyan dye-forming coupler. By applying a multilayer coating on a support, a silver halide color photographic light-sensitive material having excellent storage stability can be obtained.

The silver halide emulsion used in the light-sensitive emulsion layer of the present invention is preferably silver chlorobromide having a silver chloride content of 80 mol% or less and a silver iodide content of 1 mol% or less. The silver halide emulsion used is representative of mixed silver halides such as silver chloride and silver bromide, for example, silver chlorobromide, silver chloroiodobromide, silver iodobromide, and the halogens preferably used. Silver iodide includes silver chloroiodobromide, silver iodobromide, and silver iodide of 3 mol% or less.
It is silver chloride, silver bromide or silver chlorobromide.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention (in the case of spherical grains or grains close to spheres, the grain diameter is represented, and in the case of cubic grains, the edge length is represented by the grain size and the average based on the projected area), 0.1μ below 2μ
The above is preferable, but 1 μm or less and 0.15 is particularly preferable.
It is μ or more. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is 1.
It is preferred to use a so-called monodisperse silver halide emulsion within 5%, particularly preferably within 10% in the present invention.
Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). It is preferable that those having a variation rate) be mixed in the same layer or multilayer-coated in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention may have a regular crystal such as a cube, octahedron, dodecahedron or tetradecahedron, and may have an irregular shape such as a sphere. It may have an (irregular) crystal form, or may have a composite form of these crystal forms. Further, tabular grains may be used, and an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more account for 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsions used in the present invention are those described in Graphide, "Chemistry and Physics of Photography" [P. Glafkides, Chimie et Physique Photo.
graphique (published by Paul Montel, 1967)], “Photoemulsion Chemistry” by Duffin [Photograhic Emul by GF Duffin
sion Chemistry (published by Focal Press, 1966)], "Production and coating of photographic emulsions" by Zelikmann et al. [VL Zelikman e
t al Making and Coating Potographic Emulsin (Focal
Press, 1964)] and the like. That is, the acidic method, the neutral method,
Any method such as the ammonia method may be used, and the method of reacting the soluble silver salt and the soluble halogen salt is a one-sided mixing method,
Any of the simultaneous mixing method and the combination thereof may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As a form of simultaneous mixing method, silver halide is formed in the liquid phase.
It is also possible to use a method of keeping pAg constant, that is, a so-called controlled double jet method. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

The silver halide emulsion is usually used for coating after physical ripening, desalting and chemical ripening after grain formation.

Known silver halide solvents (e.g., ammonia, Rhodan potassium or U.S. Pat. No. 3,271,157;
No. 1-12360, JP-A No. 53-82408, JP-A No. 53-144319, JP-A No. 54-100717 or JP-A No. 54-155828. It can be used in aging and chemical aging. In order to remove the soluble silver salt from the emulsion after physical ripening, the Nudel washing, the flocculation precipitation method, the ultrafiltration method and the like are used.

The silver halide emulsion used in the present invention is a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate,
Sulfur sensitization method using thioureas, mercapto compounds, rhodanines); Reduction sensitization method using reducing substances (eg, primary tin salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); Metal compounds (eg, gold complex salts, Pt, Ir, Pd, Rh, F
A noble metal sensitization method using a complex salt of a metal of Group VIII of the periodic table such as e) can be used alone or in combination.

Photographic emulsions used in layers other than the emulsion layer of the present invention are spectrally sensitized with various photographic sensitizing dyes. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

A dye that does not have a spectral sensitizing effect by itself, or a substance that does not substantially absorb visible light, together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. For example,
Aminostilbene compounds substituted with a nitrogen-containing heterocyclic ring group (for example, US Pat. Nos. 2,933,390 and 3,6.
35,721), an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,51).
No. 0), cadmium salt, azaindene compound and the like.

Various color couplers can be used in the present invention. Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Useful color couplers are cyan, magenta and yellow color couplers, typical examples of which are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 1
7643 (Dec. 1978) Item VII-D and 18
717 (November 1979).

Among them, the general formulas (IA) and (IB) according to the present invention
Alternatively, the compound represented by (IC) and the general formula (II-A)
Alternatively, the photographic emulsion spectrally sensitized with the compound represented by (II-B) preferably contains a pyrazoloazole-based manzenta coupler described in detail later.

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The coating amount of silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted with a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. It is also possible to use couplers in which the color forming dye has a suitable diffusivity, uncolored couplers or DIR couplers which release a development inhibitor upon coupling reaction or couplers which release a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is US Pat. No. 2,40.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom releasing yellow couplers described in Nos. 2,261,361, 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while
The benzoylacetanilide coupler provides high color density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat. No. 2,311,082. Same number 2,
343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and 3,936,015.
No. etc. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat. No. 4,310,619
Nitrogen atom leaving group described in U.S. Pat.
The arylthio groups described in 51,897 are preferred. Also, a 5-pyrazolone-based coupler embryonic color density described in EP 73,636 can be obtained.

As a pyrazoloazole coupler, US Pat.
369,879, pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Lissary discloser. 24220 (1
And the pyrazolopyrazoles described in Research Disclosure 24230 (June 1984). The imidazo [1,2] described in European Patent 119,741 in view of the small yellow sub-absorption of the coloring dye and the light fastness.
-B] pyrazoles are preferred and are described in EP 119,8
No. 60 pyrazolo [1,5-b] [1,2,4]
Triazole is especially preferred.

Cyan couplers usable in the present invention include oil-protection type naphthol type and phenol type couplers, and the naphthol type couplers described in US Pat. No. 2,474,293, preferably US Pat. No. 4,05.
No. 2,212, No. 4,146,396, No. 4,2
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in Nos. 28,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Pat. No. 2,369,929 and No. 2,369,929.
801,171, 2,772,162, 2,895,826 and the like. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, of which typical examples are US Pat.
No. 72,002, a phenolic cyan coupler having an ethyl group or higher alkyl group at the meta-position of the phenol nucleus, U.S. Pat. Nos. 2,772,162 and 3,3.
758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and Japanese Patent Application No. 58-.
2,5-diacylamino-substituted phenol couplers described in US Pat. No. 4,2671, and US Pat. No. 3,44.
No. 6,622, No. 4,333,999, No. 4,4
51,559 and 4,427,767, etc., and has a phenylureido group at the 2-position and 5-
Examples thereof include phenol couplers having an acylamino group at the position.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Examples of such color-diffusion couplers include magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570, and European Patent No. 96,570 and West German Patent Application Publication No. No. 3,234,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,82.
0 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,
282.

Various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the photosensitive layer in order to satisfy the properties required for the light-sensitive material, or two or more layers in which the same compound is different. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, and examples thereof include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, a high-boiling organic solvent having a boiling point of 175 ° C. or higher and a so-called auxiliary solvent having a low boiling point are dissolved in a single liquid or a mixed liquid of both, and then water or water is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous gelatin solution. Examples of high boiling point organic solvents are US Pat.
22, 027 and the like. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, rinsing with water or ultrafiltration, and then used for coating.

Specific examples of the high boiling point organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, etc.), phosphoric acid or phosphate esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl) Phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or Phenols (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene,
Diisopropylnaphthalene, etc.) and the like. The auxiliary solvent may be an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide and the like.

The process of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. It is described in.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler and 0.003 for the magenta coupler. In the cyan coupler, it is 0.002 to 0.3 mol.

The light-sensitive material produced by using the present invention has, as a color antifoggant or color mixing inhibitor, a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamide phenol. You may contain a derivative etc.

A known anti-fading agent can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical are hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Take as an example. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

To prevent deterioration of the yellow dye image due to heat, humidity and light,
Compounds having both hindered amine and hindered phenol substructures in the same molecule, as described in US Pat. No. 4,268,593, give good results. In order to prevent the deterioration of the magenta dye image, especially the deterioration due to light,
The spiroindanes described in JP-A-56-159644 and the hydroquinone diether- or monoether-substituted chromanes described in JP-A-55-89835 give preferable results.

In the light-sensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain a stilbene-based, triazine-based, oxazole-based or coumarin-based brightening agent.
Water-soluble ones may be used, and water-insoluble whitening agents may be used in the form of dispersion.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

In addition to general-purpose lime-processed gelatin, acid-processed gelatin and “Journal of the Photographic Society of Japan” (Bull.Soc.Sci.Ph.
ot. Japan), No. 16, page 30 (1966), an enzyme-treated gelatin may be used, and a hydrolyzate or oxygen hydrolyzate of gelatin may also be used.

In the light-sensitive material of the present invention, in addition to the above-mentioned additives, various stabilizers, stain inhibitors, developers or their precursors,
A development accelerator or its precursor, a lubricant, a mordant, a matting agent, an antistatic agent, a plasticizer, or other various additives useful for a photographic light-sensitive material may be added. Typical examples of these additives are Research Disclosure 1764
3 (December 1978) and Ibid. 18716 (1979).
, November).

The present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support as described above. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support usually used for photographic light-sensitive materials such as a plastic film, paper, cloth or a rigid support such as glass, ceramics or metal. To be done.

The present invention is a color paper, a color positive film, a color negative film, a color reversal film for slides,
It can be used for general silver halide color light-sensitive materials such as color reversal films for movies and color reversal films for TV. In particular, when the present invention is used for a color paper, which is required to have excellent color reproducibility, good color image fastness, and stability to development processing, remarkable effects can be obtained.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, a p-phenylenediamine compound is preferably used, and a typical example thereof is 3-methyl-4-amino-N, N-
Diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4 -Amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates, etc. may be mentioned.

Color developers include pH buffers such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds or antifoggants. It is common to include agents and the like.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), copper (II), peracids, quinones, nitrone compounds and the like are used. Typical bleaching agents are phenyl cyanide compounds; dichromates; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid. Aminopolycarboxylic acids or complex salts of organic acids such as citric acid, tartaric acid and malic acid: persulfates; manganates; nitrosophare and the like can be used. Of these, ethylenediaminetetraacetic acid iron (II
I) Salt and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Further, the ethylenediaminetetraacetic acid iron (III) complex salt is particularly useful in both the independent bleaching solution and the one-bath bleach-fixing solution.

If necessary, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution.

After the bleach-fixing process or the fixing process, a washing process is usually performed. Various known compounds may be added to the washing process for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae and mold, magnesium salts and aluminum. A hardening agent typified by a salt, or a surfactant for preventing drying load and unevenness can be added if necessary. Or West, Photographic Science and Engineering Magazine (LEWest, Phot.Sci.Eng.), Volume 6, 344-35
The compounds described on page 9 (1965) and the like may be added. It is particularly effective to add a chelating agent or an antifungal agent.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. Furthermore, instead of the water washing step, JP-A-57 / 57
You may implement the multistage countercurrent stabilization treatment process as described in -8543. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (eg borate, etc.) for adjusting the membrane pH (eg pH 3-8).
Typical examples include metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. You can In addition, water softener (inorganic phosphoric acid,
Aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzoisothiazolinone, irithiazolone, 4-thiazoline benzimidazole, halogenated phenol, etc.), surfactant, fluorescent brightening Various additives such as agents and hardeners may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64339 and JP-A-57-144547.
No. 57-211147, No. 58-50532,
No. 58-50536, No. 58-50533, No. 58
-50534, 58-50535 and 58-
No. 115438.

Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. A temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality and the stability of the processing solution. be able to. Further, in order to save silver in the light-sensitive material, the processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath.

Example 1 The following emulsion 1 was prepared by using a silver chlorobromide emulsion composed of monodisperse cubic particles having an average particle size of 0.4 μm (silver chloride content: 30 mol%).
~ 3 were prepared. The compounds shown in Table 1 were used as spectral sensitizing dyes, and chemical sensitization was carried out by adding sodium thiosulfate in an amount of 2.0 × 10 ⁻⁵ mol per mol of silver halide. 4-hydroxy-6 as a stabilizer
300 mg of -methyl- (1,3,3a, 7) -tetrazaindene was added per mol of silver halide.

Next, 100 g of magenta coupler * a was added to anti-fading agent * b
30g, * c 20g with solvent * d 90ml, * e 60ml
And 150 ml of ethyl acetate were dissolved, and this solution was emulsified and dispersed in 1200 g of a 10% aqueous gelatin solution containing 4.0 g of sodium dodecylbenzenesulfonate to prepare Emulsion Dispersion-1. Separately, 100 g of magenta coupler * f was dissolved in a mixed solution of 200 ml of solvent * d and 100 ml of ethyl acetate together with 50 g of antifade agent * b, and this solution was added to 2000 g of 10% gelatin aqueous solution containing 8.0 g of sodium dodecylbenzenesulfonate. Emulsified and dispersed to prepare an emulsified dispersion-2. The chemical structures of the compounds * a to * f are as follows.

(* A) Magenta coupler (* B) Anti-fading agent (* C) Anti-fading agent (* D) Solvent (C ₈ H ₁₇ O ₃ P = O (* e) Solvent (* F) Magenta coupler A coating solution was prepared using the emulsions 1 to 3 and the emulsified dispersions 1 and 2 thus obtained, and coated on a double-sided polyethylene laminated paper together with a protective layer to prepare a total of 12 kinds of samples having the contents shown in Table 2. . The polyethylene on the side coated with the emulsion layer and the protective layer contains titanium dioxide and a trace amount of ultramarine.

(* G) is a hardening agent for comparison, and its chemical structure is as follows.

(* G) comparative hardener H ₂ C _{[(CH 2) 2 SO 3 CH} = CH 2 ] ₂ In order to confirm the storability of these coated samples, the change in photographic performance after storage for 4 weeks at 50 ° C.-45% RH was examined as a forced test. Before and after the sample was stored, a stretcher (Fuji Color Head 69 manufactured by Fuji Photo Film Co., Ltd.
In (0), gradation exposure for sensitometry was given through a green filter, and then development processing of the following processing steps was performed. Treatment process temperature Time Image solution 33 ° C 3.5 minutes Bleach-fix solution 33 ° C 1.5 minutes Water wash 28-35 ° C 3.0 minutes Image solution Diethylenetriamine 5 acetic acid 1.0 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Na ₂ SO ₃ 2.0 g KBr 0.5 g Hydroxylamine sulfate 3.0 g 4-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -p-phenylenediamine sulfate 5.0 g Na ₂ CO ₃ (monohydrate) 30 g Water to make 1 litter (pH 10.1) Bleach-fix solution Ammonium thiosulfate (54 wt%) 150 ml Na ₂ SO ₃ 15 g NH ₄ [Fe (EDTA)] 55 g EDTA2.2Na 4g Add water to make 1 liter (pH 6.9) Measure the color density of the treated sample and compare it with the sample before storage. The change in sensitivity after storage and the fog density of each sample were determined. The results are shown in Table 3. (For sensitivity, the sensitivity before storage is 1
00. ) According to the present invention, it can be seen that the increase in fog during storage of the product is significantly prevented.

Example 2 A color photosensitive material was prepared by coating a photosensitive layer comprising the following first to seventh layers on a paper support laminated on both sides with polyethylene. The polyethylene coated with the first layer contains titanium dioxide and a trace amount of ultramarine.

(Structure of Photosensitive Layer) The numbers corresponding to the respective components represent the coating amount expressed in units of g / m ² , and the silver halide coating amount represents the coating amount in terms of silver.

First layer (blue-sensitive layer) Silver chlorobromide emulsion (80 mol% of silver bromide) Silver 0.30 Yellow coupler (* h) 0.70 Same as above Solvent (* i) 0.15 Gelatin 0.20 Second layer (intermediate layer) Gelatin 0.90 Di-t-octylhydroquinone ... 0.05 Same as above Solvent (* j) …………… 0.10 3rd layer (green-sensitive layer) See Tables 4 and 5 4th layer (UV absorbing intermediate layer) UV absorber (* k / * l / * m) …… 0.06 / 0.25 / 0.25 Same as above Solvent (* i) ………… 0.20 Gelatin ………… 1.5 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (bromination Silver 70 mol%) ...... Silver 0.20 Cyan coupler (* n / * o) ...... 0.2 / 0.2 Coupler solvent (* i / * j) ...... 0.10 / 0. 20 Gelatin ………… 0.9 6th layer (ultraviolet absorbing intermediate layer) Ultraviolet absorber (* k / * l / * m) ………… 0.06 / 0.25 / 0.25 Same as above solvent (* j) ………… … 0.20 Gelatin ………… 1.5 1.5th layer (protective layer) Hardener See Table 5 Gelatin ………… 1.5 (* h) Yellow coupler (* I) Solvent (C ₉ H ₁₉ O * P = O (* j) Solvent (* K) UV absorber (* L) UV absorber (* M) UV absorber (* N) Cyan coupler (* O) Cyan coupler The following compounds were used as the spectral sensitizing dyes for the blue-sensitive emulsion layer and the red-sensitive emulsion layer.

Blue sensitive emulsion layer; (2 × 10 ⁻⁴ mol added per mol of silver halide.) Red-sensitive emulsion layer; (Addition of 2.5 × 10 ⁻⁴ mol per mol of silver halide.) The following dye was used as an anti-irradiation dye in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; Regarding the green-sensitive emulsion layer, first, emulsions 4 and 5 which were different from the silver halide emulsion used in Example 1 and the addition amount thereof were prepared (see Table 4). Four kinds of coating solutions were prepared by combining these with the emulsions 1 and 2 used in Example 1 and the emulsified dispersion 2 used in Example 1, and the kind of the hardener added to the protective layer was changed. Eight types of samples as shown in Table 5 were prepared.

The storability of these coated samples was examined in the same manner as in Example 1. The results are as shown in Table 6.

(Effect of the present invention) When at least two kinds of spectral sensitizing dyes of the present invention and a hardening agent are combined, it is possible to remarkably suppress the increase of fog during storage in an untreated product.

Claims (1)

[Claims] 1. A color photographic light-sensitive material comprising a support having at least one light-sensitive emulsion layer containing a silver chlorobromide emulsion (silver chloride content of 80 mol% or less) containing substantially no iodine. In at least one of the photosensitive emulsion layers, at least one of the compounds represented by the following general formula (IA), (IB), or (IC) and the following general formula (II −
A) or a silver halide emulsion spectrally sensitized by the combined use of at least one of the compounds represented by (II-B) and represented by the following general formula (III) A silver halide color photographic light-sensitive material characterized by being hardened with at least one compound and / or at least one compound represented by the following general formula (IV). General formula [IA] [IB] [IC] General formula (II-A) General formula (II-B) General formula (III) General formula (IV)