JPH0736073B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has high sensitivity and low fog, and less desensitization or increase in fog over time. The present invention relates to a silver halide color photographic light-sensitive material suitable for rapid processing.

BACKGROUND OF THE INVENTION In general, a silver halide color photographic light-sensitive material is used for three kinds of silver halide photographic materials which are selectively spectrally sensitized so that they have sensitivity to blue light, green light and red light on a support. An emulsion layer is coated. For example, in a color negative light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are generally coated in this order from the exposed side, and a blue-sensitive emulsion layer and a green-sensitive emulsion layer are provided between them. A bleachable yellow filter layer is provided to absorb blue light transmitted through the blue-sensitive emulsion layer. Further, each emulsion layer is provided with other intermediate layers for various special purposes and a protective layer as the outermost layer. Further, for example, in an exposure material for color photographic paper, a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are generally coated in this order from the side to be exposed. For the purpose, an intermediate layer such as an ultraviolet absorbing layer, a protective layer, etc. are provided. It is also known that each of these emulsion layers is provided in an arrangement different from that described above. Further, each emulsion layer is composed of two layers having photosensitivity in the substantially same wavelength range to each color light. It is also known to use emulsion layers. In these silver halide photographic light-sensitive materials, for example, an aromatic primary amine-based color developing agent is used as a color developing agent to develop exposed silver halide grains, thereby generating oxygen in the color developing agent. The dye image is formed by the reaction of the dye with the dye-forming coupler. In this method, a phenol or naphthol type cyan coupler, 5-pyrazolone, pyrazolinobenzimidazole type, pyrazolotriazole type, indazolone type or cyanoacetyl type is usually used to form dye images of cyan, magenta and yellow, respectively. Magenta couplers and acylacetamide type or benzoylmethane type yellow couplers are used. These dye-forming couplers are contained in the light-sensitive photographic emulsion layer or the developing solution. The present invention relates to a silver halide photographic light-sensitive material in which these couplers are contained in the emulsion layer in advance to make them non-spreading.

By the way, in recent years, various measures have been taken in order to rapidly perform color development. As one of the methods, it is known to use a color development accelerator when developing an exposed silver halide photographic light-sensitive material using an aromatic primary amine type color developing agent. For example, as such a color development accelerator, U.S. Pat. Nos. 2,950,970 and 2,515,147 are known.
No. 2,496,903, 4,038,075, 4,119,462,
British Patents 1,430,998, 1,455,413, JP-A-53-15831
No. 55, No. 55-62450, No. 55-62451, No. 55-62452, No. 55
-62453, 51-21422, JP51-12422, 55-49
The compounds described in No. 728 and the like were investigated, but most of these compounds have an insufficient development-accelerating effect, and even among these compounds, those showing a sufficient development-accelerating effect often cause fog. However, it was not practical.

In addition, various penetrants have been studied in order to accelerate the penetration of the color developing agent into the silver halide light-sensitive material. Among them, for example, the method of adding benzyl alcohol to the color developing solution to accelerate the color developing is widely used. Has been.

However, this method is somewhat difficult in terms of rapid processing because a sufficiently high color density cannot be obtained unless processing is performed for 3 minutes or longer at a processing temperature of 33 ° C. Further, in addition to the processing temperature, a method for color development by increasing the pH concentration of the color developing solution has also been proposed, for example, if the pH is set to 10.5 or higher,
Oxidation of color developing agents is significantly accelerated, and because there is no suitable buffer solution, color developing agents are susceptible to pH changes, which makes it difficult to obtain stable photographic performance, and processing time dependence. However, there was a problem that

On the other hand, in order to speed up color development, there is also known a method of incorporating a color developing agent into a light-sensitive material in advance as described in US Pat. No. 3,719,492.

However, this method has a drawback that the raw storability of the silver halide photographic light-sensitive material is poor and fog is generated before its use, and further fog is easily generated during color development processing.

Furthermore, in order to inactivate the amine portion of the color developing agent, for example, a method of incorporating a color developing agent into a Schiff salt is described in, for example, U.S. Pat.No. 3,342,559, Research Disclosure, 1976 No. 15159. ing. However, these methods have a drawback that the color development is delayed because the color development does not start until the color developing agent is hydrolyzed with an alkali.

Further, Japanese Patent Application Laid-Open No. 56-64339 discloses a device having a specific structure.
-Aryl-3-pyrazolidone is added to a silver halide color photographic light-sensitive material, further disclosed in JP-A-57-144547.
58-50532, 58-50533, 58-50534, 58-505
Nos. 35 and 58-50536 disclose that 1-arylpyrazolidones are added to a silver halide color photographic light-sensitive material and processed within an extremely short developing time.

However, each of the techniques described in these publications is not necessarily satisfactory in terms of obtaining a dye image having a sufficient color developing speed and a high color density, and there is still room for improvement. .

Also, in terms of other photographic performance, it is often accompanied by adverse effects such as sensitivity deterioration, softening, and increase of fog, and in terms of achieving both sufficient speedup of color development and high quality in other photographic performance. Also has a problem.

Incidentally, as the silver halide used in the silver halide photographic light-sensitive material, there are generally silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. Used. Of these, silver chlorobromide or silver chloride containing 80 mol% or more of silver chloride is excellent in rapid processing suitability, and studies on these are described in, for example, JP-A-55-135832 and JP-A-58-125,612.
It is described in JP-A-60-222,844 and British Patent 149,573. However, silver halide having 80 mol% or more of silver chloride has low sensitivity and high fog as described in the above patent, and further, desensitization and increase of fog are large with the passage of time of the sample. Known antifoggants and stabilizers such as tetrazaindenes, mercaptotriazoles, mercaptoimidazoles, catechols or resorcins have little effect, and when used in large amounts, marked desensitization occurs.

On the other hand, a silver halide photographic material (hereinafter referred to as a photographic material).
In order to prevent a filter, halation, irradiation, or to absorb light of a specific wavelength for the purpose of adjusting the sensitivity of a photographic emulsion, the hydrophilic colloid layer may be colored with a dye containing a dye in the photographic material. It is often done.

For the purpose of improving the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the surface of the support to prevent harmful effects at the interface between the emulsion layer and the support or on the back surface of the support. It is often practiced to absorb reflected light to prevent halation, or to color the emulsion layer to absorb harmful reflected light or scattered light from silver halide grains to prevent irradiation. There is.

Dyes used for such purposes have good absorption spectrum characteristics according to the purpose of use, are completely decolorized in photographic solutions, and are easily eluted from photographic materials to cause residual color after dyeing. No contamination, no adverse effects such as fog or desensitization on photographic emulsion, no diffusion from dyed layer to other layers, and in solution,
Alternatively, it must satisfy various conditions such as excellent aging stability in photographic materials and no discoloration or fading.

To date, many efforts have been made and many dyes have been proposed in order to find dyes that satisfy the above conditions. For example, oxonol dyes described in British Patent No. 506,385, U.S. Pat. There are merocyanine dyes, cyanine dyes represented by US Pat. No. 2,843,486 and the like, and further anthraquinone dyes represented by US Pat. No. 2,865,752.

Among these dyes, the bispentamethine oxonol dye that acts on the red light-sensitive emulsion layer has sharp spectral absorption characteristics, but in recent years, it has been applied to production processes or automated processes such as printers and processors of photosensitive materials. It is lacking in the ability to suppress the photosensitive fog (hereinafter referred to as infrared sensor fog) by an infrared sensitive sensor, which has become more common.

The emission wavelength of the infrared sensitive sensor varies in various ranges depending on the illuminant used, but for example, typical Ga-As
90 in Liquid Phase Epitaxial Infrared Light Emitting Diode
0 ~ 950nm, about 1140nm in the same type using Si, Ge
It is about 1880 nm in the same type using.

On the other hand, gelatin is mostly used as a binder used in a color sensitive material for printing, and a hardener for the binder is also used.

The desired properties of the hardener are that it has a rapid hardening effect, that it does not cause fog or other adverse effects on silver halide, that it has no problems in occupational health and environmental pollution, and that it is water-soluble. That is, the synthesis is easy and the cost is low.

For this reason, investigations from the hardener side such as vinyl sulfone type, ethyleneimine type, epoxy type, N-methylol type, chlorotriazine type, etc. have been promoted, and JP-B No. 47-6151 and JP-A No. 4-6151.
8-19220, 51-78788, 52-128130, 52-13032
As described in No. 6 and No. 56-1043, the chlorotriazine-based hardener almost satisfies the above-mentioned desired properties and has excellent properties.

However, this chlorotriazine-based hardener has a major drawback, which is contrary to the high productivity in recent years, that is, it acts on silver halide to lower the sensitivity, and the sensitivity is lowered with the lapse of time of the sample.

[Object of the Invention] The present invention has been made in view of such circumstances, and as a result of intensive studies on dyes and hardeners, red-sensitive silver halide having a silver chloride content of 80 mol% or more. By combining a characteristic dye and a specific hardener with the grains, it is intended to provide a silver halide color photographic light-sensitive material which meets the recent demand for high productivity with high sensitivity, low fog and suitable for rapid processing. It is a thing.

That is, a first object of the present invention is to provide a silver halide color photographic light-sensitive material suitable for rapid processing with high sensitivity and low fog.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material which is less susceptible to desensitization and increased fog over time.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material with less infrared sensor fog.

[Constitution of Invention] The above object of the present invention is to provide a silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. In the material, at least the red-sensitive silver halide emulsion layer contains silver halide grains having a silver chloride content of 80 mol% or more, and a compound represented by the following general formula [I] and / or Hardened with a compound represented by the general formula [II], the above-mentioned silver halide color photographic light-sensitive material has a maximum absorption wavelength of 660n in the gelatin film.
It is achieved by a silver halide color photographic light-sensitive material containing a water-soluble bispyrazolone pentamethine oxonol dye of m to 680 nm.

General formula [I] In the formula, R ₁ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, —OM group (M represents a monovalent metal atom), —NR′R ″ or —NHCOR (R ′,
R ″ and R each represent a hydrogen atom, an alkyl group or an aryl group), and R ₂ has the same meaning as R ₁ excluding a base atom.

General formula [II] In the formula, R ₃ and R ₄ are each a chlorine atom, a hydroxy group,
Represents an alkyl group, an alkoxy group or an -OM group (M represents a monovalent metal atom), -Q- and -Q'- represent a -O-, -S- or -NH- linking group, and L
Represents an alkylene group or an arylene group. l and m
Represents 0 or 1, respectively.

[Specific Structure of the Invention] In the present invention, at least silver halide grains contained in the red-sensitive silver halide emulsion layer (hereinafter referred to as silver halide grains according to the present invention) are 80 mol% or more of silver chloride. Has a content rate. It preferably has a silver chloride content of 90 mol% or more. The silver iodide content is 1 mol%.
It is preferably 0.5 mol% or less. More preferably, it is silver chlorobromide or silver chloride having a silver bromide content of 10% or less.

The silver halide grains according to the present invention may be used alone or in combination with other silver halide grains having different compositions. It may also be used as a mixture with silver halide grains having a silver chloride content of less than 80 mol%.

Further, silver halide grains having a silver chloride content of 80 mol% or more are all silver halide grains contained in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 80 mol% or more. Of at least 50% by weight, preferably at least 75% by weight.

The composition of the silver halide grain according to the present invention may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. When the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The grain size of the silver halide grains according to the present invention is not particularly limited, but considering other photographic performance such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably
It is in the range of 0.25 to 1.2 μm. The particle size is
It can be measured by various methods commonly used in the art. Representative methods include Loveland's "Particle Size Analysis" ASTM Symposium on Light Microscopy, 1955, pp. 94-122 and "Theory of Photographic Processes", Co-authored by Mies and James, Third Edition, Macmillan Company. It is described in Chapter 2 of the publication (1966). This particle diameter can be measured using the projected area of the particle or an approximate diameter value.
If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse. Monodisperse silver halide grains having a coefficient of variation of 0.22 or less, and more preferably 0.15 or less in the grain size distribution of silver halide grains are preferred. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

Here, ri represents the particle size of each particle, and ni represents the number. The term "particle size" used herein refers to the diameter of spherical silver halide grains, and the diameter of a cubic image or a grain having a shape other than spherical when the projected image is converted into a circular image of the same area. .

The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. In addition, US patent
4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737 and the like, and the Journal of
Photographic Science (J.Photgr. Sci), 2
By the method described in the literature such as 1 , 39 (1973), particles having a shape of octahedron, tetrahedron, dodecahedron, etc. can be prepared and used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

In the present invention, the silver halide grains used in the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer are not particularly limited, but preferably the silver halide according to the present invention, that is, the silver chloride content. Is 80 mol% or more of silver halide grains.

The silver halide grains used in the silver halide grains and the blue-sensitive silver halide emulsion layers and the green-sensitive silver halide emulsion layers according to the present invention, that is, the silver halide grains used in the present invention, are acidic methods, Those obtained by the sex method or the ammonia method may be used. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halogen salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. Furthermore, as one type of simultaneous mixing method, Japanese Patent Laid-Open No.
-48521 etc. pAg-Controlled-
The double jet method can also be used.

If necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit controlling agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grains used in the emulsion of the present invention include a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt, and an iron salt in the process of forming and / or growing the grain. Alternatively, a complex salt can be used to add a metal ion to the inside of the particle and / or to include it on the surface of the particle, and by placing in a suitable reducing atmosphere, a reduction sensitizing nucleus can be formed inside and / or on the surface of the particle. It can also be given.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. The salts can be removed by the method described in Research Disclosure No. 17643.

The silver halide grain used in the emulsion of the present invention may be a grain in which a latent image is mainly formed on the surface,
Further, particles that are mainly formed inside the particles may be used. Grains in which the latent image is mainly formed on the surface are preferable.

The emulsion of the present invention is chemically sensitized by the conventional method. That is, a sulfur-containing compound capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds. Sensing methods and the like can be used alone or in combination.

The silver halide emulsion of the present invention can be spectrally sensitized in a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Is also good.

The silver halide emulsion of the present invention includes a light-sensitive material manufacturing process,
A silver halide emulsion during and after the chemical ripening and / or after the chemical ripening for the purpose of preventing fog during storage or photographic processing and / or keeping the photographic performance stable. By the time of coating, compounds known as antifoggants or stabilizers in the photographic industry can be added.

Next, the compound represented by the general formula [I] and the compound represented by the general formula [II] will be described.

General formula [I] In the formula, R ₁ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, —OM group (M represents a monovalent metal atom), —NR′R ″ or —NHCOR (R ′,
R ″ and R each represent a hydrogen atom, an alkyl group or an aryl group), and R ₂ has the same meaning as R ₁ excluding a base atom.

General formula [II] In the formula, R ₃ and R ₄ are each a chlorine atom, a hydroxy group,
Represents an alkyl group, an alkoxy group or an -OM group (M represents a monovalent metal atom), -Q- and -Q'- represent a -O-, -S- or -NH- linking group, and L
Represents an alkylene group or an arylene group. l and m
Represents 0 or 1, respectively.

R _{1 of the} hardener represented by the above general formula [I] according to the present invention
And the alkyl group represented by R ₂ , for example, a methyl group,
An ethyl group, a butyl group and the like, and an alkoxy group represented by them are a methoxy group, an ethoxy group, a butoxy group and the like. Also Specific examples of _{-NH 2, -NHCH 3, -NHC 2} H 5 and the like, -NHCO
R As a specific example, -NHCOCH ₃ , Etc. Further, M of the —OM group represented by R ₁ and R ₂ is, for example, a sodium atom or a potassium atom.

Regarding the chlorotriazine type hardener represented by the general formula [I], U.S. Pat. No. 3,645,743, JP-B-47-6151
No. 47-33380, No. 51-9607, JP-A-48-19220,
51-78788, 52-60612, 52-128130, 52-13
No. 0326 and No. 56-1043, among which it can be used according to the above criteria.

Next, the alkyl group represented by R ₃ and R _{4 in} the general formula [II] is, for example, a methyl group, an ethyl group, a butyl group, etc., and the alkoxy group is a methoxy group, an ethoxy group, a butoxy group, etc. M of the group is, for example, a sodium atom, a potassium atom or the like.

The alkylene group represented by L is, for example, —CH ₂ —, — (CH
₂ ) ₂ −, — (CH ₂ ) ₃ groups and the like, and the arylene group is, for example, p
And a-, o- or m-phenylene group.

Regarding the chlorotriazine-based hardener represented by the general formula [I], Canadian Patent 895,808, JP-B-58-33542
JP-A-57-40244 and the like, and they can be selected for use based on the above criteria.

At least one hardener selected from the compounds represented by the above general formula [I] or [II] according to the present invention hardens the red light-sensitive silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention. As long as it can be added to any layer, it is preferably a protective layer.

The method for adding the hardener used in the present invention is to dissolve the hardener of the present invention in water or alcohol (eg, methyl alcohol, ethyl alcohol, etc.) and apply it to 1 g of coated gelatin.
0.5 to 100 mg, preferably 2 to 50 mg may be added. The addition method may be either a batch method or an in-line method.

The hardener represented by the general formula [I] or [II] according to the present invention is a vinyl sulfone-based hardener described in US Pat. No. 3,490,911 and West German Patent 2,749,260, US Pat. No. 2,950,197,
No. 2,804,404, No. 2,983,611, No. 3,271,175, Japanese Patent Publication No. 46-40898, and aldehyde hardeners described in JP-A No. 50-91315, aziricin hardeners, or U.S. Patent No. 3,047,394, West Germany. Patent 1,085,663, British Patent 1,033,
It may be used in combination with an epoxy hardener such as those described in JP-A No. 518 and JP-B-48-35495, and is particularly preferably used in combination with a vinyl sulfone hardener. When the hardener of the present invention and the vinyl sulfone-based hardener are combined, the ratio is preferably 1: 0.2 to 1: 5.0 (weight).

Typical specific examples of the compound represented by the formula [I] or [II] are shown below, but the present invention is not limited thereto.

Compound represented by general formula [HI]: Compound represented by general formula [H-II]: The bispyrazolone pentamethine oxonol dye according to the present invention can be selected by measuring the spectral absorption maximum in the gelatin film by the method described below. That is, a dye is dissolved in a 5% aqueous solution of alkali-treated ossein gelatin so as to be 0.01%, and then coated on a transparent support so that the gelatin coating amount is 5 g / m ₂ and the dye coating amount is 10 μg / m _2. After drying, the spectral absorption concentration is measured and the absorption maximum wavelength is determined. A dye having an absorption maximum wavelength of less than 660 nm or a dye having a maximum absorption wavelength of 680 nm or more causes large desensitization with time.

Next, the general formula [III] preferably used in the present invention
The dye represented by will be described.

General formula [III] In the formula, R ₅ and R ₆ each represent --CN or --COOR ₉ and R
₉ represents an alkyl group or an aryl group. L represents a methine group. Particularly preferably R ₅ and R ₆ are -CN.

R ₇ and R ₈ each represent an aliphatic group, an aromatic group or a heterocyclic group.

In the general formula [III], -C represented by R ₅ and R ₆
R ₉ of OOR ₉ represents an alkyl group or an aryl group, and the alkyl group and the aryl group include those having a substituent. Examples of the alkyl group include methyl, ethyl, hydroxyethyl, cyanoethyl, hydroxyethoxyethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, octyl, decyl, dodecyl, pentadecyl, octadecyl, benzyl and the like. Further, examples of the aryl group include substituted and unsubstituted phenyl, tolyl, ethylphenyl, chlorophenyl, methoxyphenyl, naphthyl and the like.

R ₇ and R ₈ each represent an aliphatic group, an aromatic group or a heterocyclic group. Among them, the aliphatic group is an alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group). Group, octyl group, dodecyl group etc.), cycloalkyl group (eg cyclohexyl group etc.), alkenyl group (eg butenyl group etc.). Representative examples of the aromatic group include an aryl group such as a phenyl group and a naphthyl group. Further, as the heterocyclic group, for example, a benzthiazolyl group and a benzoxazolyl group can be mentioned as typical ones.

The aliphatic group, aromatic group and heterocyclic group represented by R ₇ and R ₈ further include a hydroxy group, an amino group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkoxy group (for example, Methoxy group, ethoxy group, etc.), carboxy group, carbamoyl group, sulfo group, sulfamoyl group, aryl group (eg phenyl group, 4-sulfophenyl group etc.), aryloxy group (eg phenoxy group, 4
-Sulfophenoxy group etc.) and the like.
Further, the aryl group may be substituted with an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, etc.).

Furthermore, examples of the aryl group represented by R ₇ and R ₈ having a sulfo group include 4-sulfophenyl group, 3-sulfophenyl group, 2-methyl-4-sulfophenyl group, and 2
-Chloro-4-sulfophenyl group, 4-chloro-3-sulfophenyl group, 2-chloro-5-sulfophenyl group,
2-methoxy-4-sulfophenyl group, 2-hydroxy-4-sulfophenyl group, 2,5-dichloro-4-sulfophenyl group, 2,6-dimethyl-4-sulfophenyl group,
2,5-disulfophenyl group, 3,5-disulfophenyl group,
4-phenoxy-3-sulfophenyl group, 2-chloro-
6-methyl-4-sulfophenyl group, 3-carboxy-
2-hydroxy-5-sulfophenyl group, 3,6-disulfo-α-naphthyl group, 8-hydroxy-3,6-disulfo-α-naphthyl group, 5-hydroxy-7-sulfo-β-
Examples thereof include a naphthyl group and a 6,8-disulfo-β-naphthyl group. Furthermore, examples of the heterocyclic group of R ₃ and R ₄ substituted with a sulfo group include 2- (6-sulfo)
Examples thereof include a benzthiazolyl group and a 2- (6-sulfo) benzoxazolyl group.

The sulfo group may be bonded to the aryl group via a divalent organic group, and examples thereof include a 4- (4-sulfophenoxy) phenyl group, a 4- (2-sulfoethyl) phenyl group, and a 3- (sulfo group. Methylamino) phenyl group, 4- (2
-Sulfoethoxy) phenyl group may be mentioned.

Examples of the aryl group represented by R ₇ and R ₈ include carboxyphenyl, 3,5-dicarboxyphenyl and 3,5-disulfophenyl-3-carboxy-4-hydroxy-5-sulfophenyl.

The methine group represented by L is substituted with an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, isopropyl group, tertiary butyl group, etc.) or aryl group (eg, phenyl group, tolyl group, etc.). May be done.

Of the above R ₅ and R _6, a —CN group is preferred. Further, among R ₇ and R ₈ , an aromatic group is preferable, and a 4-sulfophenyl group and a 2,5-di-sulfophenyl group are particularly preferable.

Representative specific examples of the dye of the present invention represented by the general formula [III] are shown below, but the dye of the present invention is not limited thereto.

The dye represented by the general formula [III] has the following general formula [I
II-A] and a 3-cyano-5-pyrazolone body,
The following general formulas [III-B], [III-C], [III-D]
Alternatively, it can be synthesized by reacting with a compound represented by [III-E] in the presence of a base.

General formula [III-A] General formula [III-B] General formula [III-C] HC (OR ') ₃ General formula [III-D] General formula [III-E] In the formula, R ₃ , L and n have the same meanings as those in the general formula [III], and G represents a hydrogen atom, a halogen atom (for example,
Fluorine atom, chlorine atom, bromine atom) or a monovalent organic group, trifluoromethyl group, ethoxycarbonyl group and the like. X represents an anion (for example, chloride, bromide, iodide, perchlorate, p-toluenesulfonate, methylsulfonate, ethylsulfonate, etc.), and m represents 0 or 1. R '
Represents a methyl group or an ethyl group.

As the base to be present, pyridine, piperidine,
Triethylamine, triethanolamine, morpholine, ammonia, etc. are used.

As the solvent for the compound, alcohols (eg, methanol, ethanol, etc.), ethylene glycol, ethylene glycol monoalkyl ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl alcohol, etc.), acetonitrile, dimethyl sulfoxide, amides ( For example, dimethylformamide, dimethylacetamide, acetamide, etc.) is used.

The reaction is suitably carried out at a temperature from 0 ° C. to the boiling point of the solvent used, and the reaction formula [III-
The 3-cyano-5-pyrazolone body represented by A] has the general formula [III-B], [III-C], [III-D] or [III
It is suitable to use about twice the molar amount of the compound represented by the formula [E].

Further, the 3-cyano-5-pyrazolone body represented by the general formula [III-A] can be synthesized by utilizing the production method described in British Patent No. 585,780.

The synthesis of the oxonol dye of the present invention will be specifically described below with reference to synthesis examples.

Synthesis Example 1 (Synthesis of Exemplified Dye (III-1)) 1- (4′-sulfophenyl) -3-cyano-5-pyrazolone 10.6 g and glutacondialdehyde dianyl hydrochloride
5.7g and put in 100ml of dimethylformaldehyde,
Further, 6.1 g of triethylamine was added, and the mixture was stirred at room temperature for 4 hours. Next, 5.9 g of potassium acetate dissolved in 150 ml of methanol was added and stirred. The precipitated dye crystals were collected by filtration, washed with acetone, then with methanol, and dried to obtain 9.7 g of dye. The λmax of the aqueous solution of this dye is 6
It was 45 nm.

Further, the exemplified dyes III-6 and III-8 to III-16 are disclosed in JP-A-SHO.
It is manufactured according to the method described in 48-62826. Typical examples are shown below.

Synthesis Example 3 (Synthesis of Dye III-13) 1- (4'-sulfophenyl) -3-carbethoxy-
A dye of green-blue crystals was obtained in the same manner as in Synthesis Example 2 using 5-pyrazolone and glutacondialdehyde dianyl hydrochloride. An aqueous solution of 1 / 200,000 parts by weight of this dye is blue and has a λma
x was 645 mμ and its D was 0.68.

In the silver halide photographic light-sensitive material of the present invention, the dye represented by the general formula [III] may be contained in any of the light-sensitive emulsion layer or the non-light-sensitive layer of the silver halide photographic light-sensitive material. Is used in the red light-sensitive silver halide emulsion layer of the present invention or in the non-light-sensitive layer adjacent thereto.

Further, two or more kinds of dyes according to the present invention may be used depending on the purpose of use, or may be used in combination with other dyes.
To incorporate the dye according to the present invention in the silver halide photographic emulsion layer or other hydrophilic colloid layer, the dye or an organic / inorganic alkali salt of the dye is generally used in an aqueous solution or an organic solvent (for example, alcohol). , Glycols, cellosolves, dimethylformaldehyde, dibutyl phthalate, tricresyl phosphate, etc.), and if necessary emulsify and disperse, add to the coating solution and apply to the silver halide photographic light-sensitive material. Dyes can be included. The content of these dyes varies depending on the purpose of use, but generally 0.01 to 0.5 mg / dm
₂ , preferably 0.03 to 0.2 mg / dm ₂ so as to be applied.

When the dye according to the present invention is used in combination with other dyes other than the present invention, particularly preferable dyes include U.S. Pat.
Anthraquinone dyes represented by the following general formula [VI] represented by No. 2,865,752 and the like.

General formula [VI] In formula [VI], R ₁ , R ₄ , R ₅ and R ₈ are each a hydrogen atom, a hydroxy group, a -RO group or Represents Here, R represents an alkyl group or an aryl group, R ′ and R ″ represent a hydrogen atom or an alkyl group or an aryl group having at least one sulfonic acid group or carboxylic acid group, and R ₂ , R ₃ or R ₆ And R ₇ each represent a hydrogen atom, a carboxylic acid group, a sulfonic acid group, or an alkyl group or an aryl group having at least one carboxylic acid group or sulfonic acid group.

The alkyl group represented by R of the —OR group represented by R ₁ , R ₄ , R ₅ and R _{8 in} the general formula [VI] is, for example, a methyl group, an ethyl group or a butyl group, and the aryl group represented by R is, for example, It is a phenyl group. The alkyl group having at least one sulfonic acid group or a carboxylic acid group represented by the -NR'R "R radicals' and R" for example _{-CH 2 SO 3 H, - (} CH 2) 2 SO 3 H, -
CH ₂ COOH,-(CH ₂ ) ₂ COOH or its sodium salt, potassium salt or ammonium salt. The aryl group represented by R ′ and R ″ is, for example, Etc.

The alkyl group or aryl group having at least one carboxylic acid group or sulfonic acid group represented by R ₂ , R ₃ , R ₆ and R ₇ may be the same as those represented by R ′ and R ″. it can.

Compound represented by the general formula [VI] is used dissolved in normal water or alcohol, the amount added is 1 to 100 mg / m ₂ in the photosensitive material, preferably so as to be 5 to 50 mg / m ₂ Added.

When used in combination with the dye of the present invention, the use ratio of the dye of the present invention to the anthraquinone dye is preferably 1: 0.5 to 1: 4 by weight.

Next, typical specific examples of the compound represented by the above general formula [VI] will be given.

Next, the sensitizing dye represented by the general formula [IV] or [V], which is preferably used in the invention, will be described.

General formula [IV]General formula [V]Where R_FiveAnd R₆Is an alkyl group or aryl
Represents a group, L₁, L₂, L₃, L_FourAnd L_FiveRepresents a methine group
You Z₁And Z₂Are oxazole ring and thiazole, respectively
Atoms necessary to complete the ring or selenazole ring or
Represents a group of atoms. Z₃Is a necessary hydrocarbon to form a 6-membered ring
Represents a group of atoms. X Represents an acid anion. m₁, M₁,
n and l₁Represents 0 or 1, respectively. However
When the compound forms an inner salt, l is 0.

In the general formulas [IV] and [V], the alkyl group represented by R ₅ and R ₆ may be branched or may have an unsaturated bond. More preferably, it has 10 or less carbon atoms and has an atom or a substituent such as sulfo, aryl, carboxy, amine (primary, secondary, tertiary), alkoxy, aryloxy, hydroxy, alkoxycarbonyl, acyloxy and halogen. You may have.
Specific examples include methyl group, ethyl group, sulfobutyl group,
Benzyl group, phenethyl group, carboxymethyl group, dimethylaminopropyl group, methoxyethyl group, phenoxypropyl group, methylsulfonylethyl group, cyclohexyl group, octyl group, decyl group, carbamoylethyl group,
Sulfophenethyl group, sulfobenzyl group, 2-hydroxy-3-sulfopropyl group, ethoxycarbonylethyl group, 2,3-disulfopropoxypropyl group, sulfopropoxyethoxyethyl group, trifluoroethyl group, carboxybenzyl group, cyanopropyl Group, p-carboxyphenethyl group, ethoxycarbanylmethyl group, pivaloylpropyl group, propionylethyl group, anisyl group, acetoxyethyl group, benzoyloxypropyl group, chloroethyl group, N-ethylaminocarbonylpropyl group,
An allyl group, a 2-butynyl group, a cyanoethyl group and the like.

The aryl group represented by R ₅ and R ₆ is, for example, a phenyl group, a carboxyphenyl group, a sulfophenyl group, or the like.

When the methine group represented by L ₁ , L ₂ and L ₃ has a substituent, it is represented by the formula (-CR =), and the substituent R is a linear or branched alkyl group having about 1 to 8 carbon atoms. Group (eg methyl group, ethyl group, carboxymethyl group, benzyl group), alkoxy group (eg methoxy group, ethoxy group)
And aryl groups (eg, phenyl group, tolyl group) and the like.

Specific examples of the thiazole nucleus, the selenazole nucleus or the oxazole nucleus completed by Z ₁ and Z _{2 of the} general formulas [IV] and [V] include thiazole, 4-methylthiazole, 5-phenylthiazole, 4,5- Dimethylthiazole, benzothiazole, 5-chlorobenzothiazole,
6-chlorobenzothiazole, 3-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-butylbenzothiazole, 5 -Pivaloylaminobenzothiazole, 6-benzoylaminobenzothiazole, 5-acetylbenzothiazole,
6-acetylaminobenzothiazole, 5-phenylbenzothiazole, 6-methoxybenzothiazole, 5-
Iodobenzothiazole, 5-methoxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 5-
Phenoxybenzothiazole, 5-phenethylbenzothiazole, 5-cyanobenzothiazole, naphtho [1,2
-D] thiazole, naphtho [2,1-d] thiazole, naphtho [2,3-d] thiazole, 5-ethoxynaphtho [1,2
-D] thiazole, 8-methoxynaphtho [2,1-d] thiaoxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d] oxazole, etc. Can be mentioned.

The acid anion represented by X in the general formulas [IV] and [V] is, for example, chlorine ion, bromine ion, iodine ion, perchlorate ion, fluoroborate ion, p-toluenesulfonate ion, ethylsulfonate ion. , Nitrate ions and the like.

Further, among the sensitizing dyes represented by the above general formulas [IV] and [V], particularly useful sensitizing dyes can be represented by the following general formulas [IVa] and [Va].

General formula [IVa] General formula [Va] In the formula, Y ₁ and Y ₂ each represent an oxygen atom, a sulfur atom or a selenium atom, and R ₁₀ and R ₁₁ each represent a lower alkyl group.

A ₁ , A ₂ , B ₁ , B ₂ , C ₁ , C ₂ , D ₁ and D ₂ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a cyano group, a nitro group or an alkoxycarbonyl group. Represent. Also, A ₁ and B ₁ , B ₁ and C ₁ , C ₁ and D ₁ , A ₂ and B ₂ ,
At least one of the combinations of B ₂ and C ₂ and C ₂ and D ₂ may be condensed to form a benzene ring.

A ₁ , A ₂ , B ₁ , B ₂ , C _{1 of} the general formulas [IVa] and [Va],
The alkyl group represented by C ₂ , D ₁ and D ₂ is a linear or branched lower alkyl group having about 1 to 5 carbon atoms (eg, methyl group, ethyl group, butyl group, trifluoromethyl group). The alkoxy group is a linear or branched alkyloxy group having about 1 to 5 carbon atoms (eg, methoxy group, ethoxy group), the halogen atom is fluorine, chlorine, bromine or iodine, and the phenyl group is For example, it is a phenyl group having no substituent, a hydroxyphenyl group, or a carboxyphenyl group, and the alkoxycarbonyl group is, for example, a methoxycarbonyl group or an ethoxycarbonyl group.

R_Five, R₆, L₁, L₂, L₃, L_Four, L_Five, X , N and l₁Is it
Each of the formulas described in the above general formulas [IV] and [V]
Are synonymous. However, it is more preferable that n is 1.
Yes.

Specific examples of the sensitizing dye represented by the general formula [IV] or [V] are shown below, but the sensitizing dye that can be used in the present invention is not limited to these.

The sensitizing dye represented by the general formula [IV] or [V] according to the present invention may be added at any time during the emulsion production process, but is preferably during or after chemical ripening, and more preferably chemical ripening. Add during aging. The addition amount is 10 _-7 to 10 _-3 mol, preferably 5 per mol of silver halide.
It is from × 10 _{-6 to} 5 × 10 _-4 mol.

When the silver halide grains contained in the red-sensitive silver halide emulsion layer are color-sensitized with the sensitizing dye represented by the above general formula [IV] or [V], the desensitization with high sensitivity can be achieved with time. The effect of the present invention, which is small, can be further enhanced.

The silver halide photographic light-sensitive material of the present invention can be, for example, a negative and a positive film of a color negative, a color photographic paper, and the like. In particular, when the color photographic paper used for direct viewing is used, the method of the present invention can be used. The effect of is effectively exhibited.

The silver halide photographic light-sensitive material of the present invention, including this color photographic paper, may be monochromatic or polychromatic. In the case of a multi-color silver halide photographic light-sensitive material, it is usually used as a photographic coupler in order to perform color reduction method color reproduction.
It has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers and a non-photosensitive layer are laminated on a support in an appropriate number of layers and layer order. The order may be appropriately changed depending on the priority performance and purpose of use.

When the silver halide photographic light-sensitive material of the present invention is a multicolor color light-sensitive material, the specific layer structure is as follows: from the support side to the yellow dye image forming layer, the intermediate layer, and the magenta dye of the present invention. Those in which the image forming layer, the intermediate layer, the cyan dye image forming layer, the intermediate layer and the protective layer are arranged are particularly preferable.

As described above, the red-sensitive silver halide emulsion has the general formula [IV]
Alternatively, it is preferable to perform color sensitization with a sensitizing dye represented by [V], but silver halide emulsion agents other than red-sensitive dyes can also be obtained by using dyes known as sensitizing dyes in the photographic industry. Can be optically sensitized to the wavelength range of. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Is also good.

The silver halide emulsion of the present invention includes a light-sensitive material manufacturing process,
A silver halide emulsion during chemical ripening for the purpose of preventing fog during storage or during photographic processing and / or for maintaining stable photographic performance, and / or at the end of chemical ripening and / or after the end of chemical ripening. By the time of coating, compounds known as antifoggants or stabilizers in the photographic industry can be added.

As the binder (or protective colloid) of the silver halide emulsion of the present invention, it is advantageous to use gelatin,
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers or copolymers can also be used.

A light-sensitive material using the silver halide emulsion of the present invention A plasticizer can be added for the purpose of enhancing the flexibility of the silver halide emulsion layer and / or other hydrophilic colloid layer.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains a dispersion (terax) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. Can be done.

In the color development processing, the emulsion layer of the silver halide color photographic light-sensitive material of the present invention is subjected to a coupling reaction with an oxidant of an aromatic primary amine developer (for example, p-phenylenediamine derivative or aminophenol derivative). Dye-forming couplers are used that form dyes that do. The dye-forming couplers are usually selected for each emulsion layer so that a dye is formed which absorbs the light in the light-sensitive spectrum of the emulsion layer, and the blue-light-sensitive emulsion layer contains a yellow dye-forming coupler. A magenta dye-forming coupler is used for the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used for the red light-sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

As the yellow dye-forming coupler, known acylacetanilide type couplers can be preferably used.
Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include British Patent No. 1,077,874, Japanese Patent Publication No. 45-40757, JP-A Nos. 47-1031, 47-26133, and 4
8-94432, 50-87650, 51-3631, 52-115219
No. 54-99433, No. 54-133329, No. 56-30127, U.S. Patent Nos. 2,875,057, 3,253,924, 3,265,506.
No. 3,408,194, 3,551,155, 3,551,156,
3,64,841, 3,725,072, 3,730,722, 3,8
91,445, 3,900,483, 3,929,484, 3,933,50
No. 0, 3,973,968, 3,990,896, 4,012,259,
4,022,620, 4,029,508, 4,057,432, 4,1
06,942, 4,133,958, 4,269,936, 4,286,05
No. 3, No. 4,304,845, No. 4,314,023, No. 4,336,327,
No. 4,356,258, No. 4,386,155, No. 4,401,752, etc.

As the yellow dye-forming coupler used in the blue light-sensitive emulsion layer, a coupler represented by the following general formula [Y] can be preferably used.

General formula [Y] In the formula, R ₁ represents a halogen atom or an alkoxy group. R ₂
Represents a hydrogen atom, a halogen atom or an alkoxy group which may have a substituent. R ₃ is an optionally substituted acylamino group, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an arylsulfonamide group, an alkylureido group, an arylureido group, a succinimide group, an alkoxy group or Represents an aryloxy group. Z ₁ represents a group which can be released upon coupling with the oxidized product of the color developing agent.

Specific examples of the yellow dye-forming coupler are shown below.

[Exemplified compound]

As the magenta dye-forming coupler used in the green light-sensitive emulsion layer, couplers represented by the following general formulas [a] and [aI] can be preferably used.

General formula [a] [In the formula, Ar represents an aryl group, Ra ₁ represents a hydrogen atom or a substituent, and Ra ₂ represents a substituent. Y represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent, W represents -NH-, -NHCO- (N atom is bonded to carbon atom of pyrazolone nucleus) or -NHCONH-, m is an integer of 1 or 2. ) Specific example of [a] Formula [aI] Formula [aI] In the magenta coupler represented by, Za represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Za may have a substituent.

X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent.

Ra represents a hydrogen atom or a substituent.

As the substituent represented by Ra, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, organic hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group , Carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples thereof include an alkylthio group, an arylthio group and a heterocyclic thio group.

These are, for example, U.S. Patent Nos. 2,600,788 and 3,061,4.
No. 32, No. 3,062,653, No. 3,127,269, No. 3,311,
No. 476, No. 3,152,896, No. 3,419,391, No. 3,51
No. 9,429, No. 3,555,318, No. 3,684,514, No. 3,8
88,680, 3,907,571, 3,928,044, 3,
930,861, No. 3,930,866, No. 3,933,500, etc., JP-A-49-29639, 49-111631, 49-129538
No. 50, No. 50-13041, No. 52-58922, No. 55-62454, No. 55
-118034, 56-38043, 57-35858, 60-23855
Publications, British patent 1,247,493, Belgian patent 7
No. 69,116, No. 792,525, West German Patent No. 2,156,111, JP-B-46-60479, JP-A-59-125,732, 59-2.
28,252, 59-162,548, 59-171,956, 60-33,
Nos. 552 and 60-43,659, West German Patent 1,070,030, and US Pat. No. 3,725,067 are described.

Typical examples of cyan dye-forming couplers include phenol-based and naphthol-based 4-equivalent or 2-equivalent cyan dye image-forming couplers, and US Pat.
No. 2,356,475, No. 2,362,598, No. 2,367,531, No. 2,369,929, No. 2,423,730, No. 2,474,293,
No. 2,476,008, No. 2,498,466, No. 2,545,687
No. 2, No. 2,728,660, No. 2,772,162, No. 2,895,82
No. 6, No. 2,976,146, No. 3,002,836, No. 3,419,3
No. 90, No. 3,446,622, No. 3,476,563, No. 3,737,
No. 316, No. 3,758,308, No. 3,839,044, British Patent No. 478,991, No. 945,542, No. 1,084,480, No.
1,377,233, 1,388,024 and 1,543,040, as well as JP-A-47-37425, 50-10135, and
50-25228, 50-112038, 50-117422, 50-130
No. 441, No. 51-6551, No. 51-37647, No. 51-52828, No. 51-52828
51-108841, 53-109630, 54-48237, 54-661
No. 29, No. 54-131931, No. 55-32071, No. 59-146,050
No. 59-31,953 and No. 60-117,249.

As the cyan-forming coupler, the following general formulas [E] [F]
The coupler represented by is preferably used.

General formula [E] In the formula, R ₁ represents an aryl group, a cycloalkyl group or a heterocyclic group. R ₂ represents an alkyl group or a phenyl group. R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Z ₁ represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent.

General formula [F] In the formula, R ₄ represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.). R ₅ represents an alkyl group (eg, methyl group, ethyl group, etc.). R ₆ is a hydrogen atom, a halogen atom (eg fluorine, chlorine, bromine etc.) or an alkyl group (eg methyl group, ethyl group etc.)
Represents Z ₂ represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine type color developing agent.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed on the surface of silver halide crystals, various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, and the like can be used. It can be appropriately selected depending on the chemical structure of the hydrophobic compound. The oil-in-water emulsion dispersion method can be a method of dispersing a hydrophobic additive such as a coupler, and is usually a high-boiling organic solvent having a boiling point of about 150 ° C. or higher, if necessary, a low-boiling point, and / or a water-soluble organic solvent. Dissolved in combination with a solvent, and emulsified and dispersed using a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flowgit mixer, and an ultrasonic device. After that, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

As a high-boiling point oil agent, a phenol derivative that does not react with an oxidized product of a developing agent, a phthalic acid ester, a phosphoric acid ester, a citric acid ester, a benzoic acid ester, an alkylamide,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150 ℃
The above organic solvents are used.

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, A cationic surfactant can be used.

Between the emulsion layers of the photographic light-sensitive material of the present invention (same color-sensitive layers and / or different color-sensitive layers), an oxidant of a developing agent or an electron transfer agent moves to cause color turbidity or deterioration of sharpness. In order to prevent the graininess from being conspicuous, a color antifoggant is used.

The color antifoggant may be used in the emulsion layer itself, or may be used in the intermediate layer by providing an intermediate layer between adjacent emulsion layers.

An image stabilizer which prevents deterioration of a dye image can be used in a light-sensitive material using the silver halide emulsion of the present invention.

The protective layer of the light-sensitive material of the present invention, a hydrophilic colloid layer such as an intermediate layer to prevent fog due to discharge due to the light-sensitive material being charged by friction or the like, and an ultraviolet absorber to prevent deterioration of the image by UV light. It may be included.

The silver halide emulsion layer of the silver halide photographic light-sensitive material using the silver halide emulsion of the present invention, and / or other hydrophilic colloid layers are used to reduce the gloss of the light-sensitive material, enhance the writing property, A matting agent can be added for the purpose of preventing sticking.

A lubricant may be added to reduce the sliding friction of the photographic light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of antistatic can be added to a light-sensitive material using the silver halide emulsion of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used to protect the emulsion layer and / or the emulsion layer on the side of the support other than the emulsion layer. It may be used for the colloid layer.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention, the coating property is improved,
Various surfactants are used for the purpose of preventing static charge, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (such as acceleration of development, hardening, and sensitization).

The light-sensitive material using the silver halide emulsion of the present invention is a photographic emulsion layer, the other layers are baryta paper or paper laminated with α-olefrein polymer, a flexible reflective support such as synthetic paper, cellulose acetate, nitric acid. Cellulose, polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, and rigid bodies such as glass, metal and pottery.

The silver halide material of the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment or the like on the surface of the support, if necessary, directly or ((adhesiveness of support surface, antistatic property, dimensional stability,
It may be applied via one or more subbing layers (to improve wear resistance, hardness, antihalation, frictional properties, and / or other properties).

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As the light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam,
Any known light source such as light emitted from a phosphor excited by X-rays, γ-rays or α-rays can be used.

The exposure time is, of course, from 1 millisecond to 1 second which is usually used in a camera, and it is also possible to use exposure shorter than 1 microsecond, for example, 100 microsecond to 1 microsecond using a cathode ray tube or a xenon flash lamp. However, exposure longer than 1 second is possible. The exposure may be performed continuously or intermittently.

The silver halide photographic light-sensitive material of the present invention can form an image by performing color development processing known in the art.

The color developing agent used in the color developing solution in the present invention includes known ones widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Also, these compounds generally have a concentration of about 0.1 g to about 30 g, preferably Color Developer 1 for Color Developer 1.
Is used at a concentration of about 1 g to about 15 g.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-Oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful primary aromatic amine color developing agents are N, N'-
A dialkyl-p-phenylenediamine compound,
The alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include
N, N'-diethyl-p-phenylenediamine hydrochloride, N
-Methyl-p-phenylenediamine hydrochloride, N, N'-dithymer-p-phenylenediamine hydrochloride, 2-amino-
5- (N-ethyl-N-dodecylamino) -toluene,
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate, N-ethyl-N
-Β-hydroxyethylaminoaniline, 4-amino-
3-methyl-N, N'-diethylaniline, 4-amino-
Examples thereof include N- (2-methoxyethyl) -N-ethyl-3-methylaniline and -p-toluenesulfonate.

A well-known developer component compound can be added to the color developing solution applied to the processing of the silver halide photographic light-sensitive material of the present invention, in addition to the above-mentioned first primary aromatic amine color developing agent. For example, alkali agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites,
Alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol,
A water softening agent and a thickening agent may be optionally contained.

The pH value of the color developer is usually 7 or higher, most commonly about
10 to about 13.

The silver halide photographic light-sensitive material according to the present invention can contain these color developing agents as the color developing agent itself or as a precursor thereof in the hydrophilic colloid layer, and can be processed with an alkaline activating bath. The color developing agent precursor is a compound capable of forming a color developing agent under alkaline conditions, and a shift base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, Examples include sugar amine reactant precursors and urethane type precursors.
These precursors of aromatic primary amine color developing agents are disclosed, for example, in U.S. Pat. Nos. 3,342,599 and 2,507,114.
No. 2,695,234, No. 3,719,492, British Patent No. 803,78
No. 3, each specification, JP-A Nos. 53-185628 and 54-79035, Research Disclosure 15159, 121
46 and 13924.

It is necessary to add these aromatic primary amine color developing agents or their precursors so that a sufficient amount of color can be obtained only by the amount when activated. This amount varies greatly depending on the kind of the light-sensitive material, but it is generally between 0.1 and 5 mol, preferably 1 mol, per mol of silver halide.
It is used in the range of 0.5 mol to 3 mol. These color developing agents or their precursors can be used alone or in combination. Water to incorporate in the photosensitive material,
It can also be added by dissolving it in an appropriate solvent such as methanol, ethanol or acetone, or can be added as an emulsified dispersion using a high boiling point organic solvent such as dibutyl phthalate, dioctyl phthalate or trichlorylyl phosphate. It can also be added by impregnating a latex polymer as described in Disclosure No. 14850.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. Many compounds are used as bleaching agents, among which iron (III), cobalt (III), copper (II)
Polyvalent metal compounds, especially complex salts of these polyvalent metal cations with organic acids, for example aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotritriacetic acid, N-hydroxyethylethylenediaminediacetic acid, malonic acid,
Metal complex salts such as tartaric acid, malic acid, diglycolic acid and dithioglycolic acid, or ferricyanates, dichromates and the like may be used alone or in an appropriate combination.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea and thioether.

After the fixing process, a washing process is usually performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed, or both may be used in combination. The stabilizing solution used in the stabilizing treatment may contain a pH adjusting agent, a chelating agent, a anti-violent agent and the like. For these specific conditions, reference can be made to JP-A-58-134,636.

[Specific effects of the invention] According to the present invention, by combining a specific dye and a specific hardener with red-sensitive silver halide grains having a silver chloride content of 80 mol% or more, high sensitivity and low fog can be obtained. It is possible to obtain a silver halide photographic light-sensitive material suitable for rapid processing and satisfying the recent demand for high productivity.

Furthermore, it is possible to obtain a silver halide photographic light-sensitive material capable of printing with high yield, with less desensitization and increase in fog with time.

[Specific Examples of the Invention] The present inventors conducted various experiments in order to confirm the effects of the present invention. Typical examples are shown below. The present invention is not limited to these examples.

Example 1 The following 1st to 7th layers were coated on a reflective support made of polyethylene-coated paper to prepare 14 kinds of samples in total.

First layer: Blue-sensitive silver chloride emulsion layer A silver chloride emulsion formed by blue-sensitizing silver chloride grains having an average grain size of 0.8 μm, and a yellow coupler (Y-29) and 2,5
It was applied using an emulsion dispersion prepared by dissolving -di-t-octyl hydroquinone in dioctyl phthalate.

Second layer: first intermediate layer Coating was carried out using an emulsion dispersion prepared by dissolving 2,5-di-t-octylhydroquinone in dioctylphthalate.

Third layer: green light-sensitive silver chlorobromide emulsion layer A silver chloride emulsion formed by sensitizing silver chloride grains having an average grain size of 0.5 μm in green, and magenta couplers (m-5) and 2,5
It was applied using an emulsion dispersion prepared by dissolving -di-t-octyl hydroquinone in dioctyl phthalate.

4th layer ... 2nd intermediate layer The following ultraviolet absorber (UV-1) and 2,5-di-t-octylhydroquinone were dissolved in dioctylphthalate to form an emulsion dispersion, which was applied.

Fifth layer: red-sensitive silver chlorobromide or silver chloride emulsion layer Silver chlorobromide particles containing silver chloride and having an average particle size of 0.5 μm shown in Table 2 or an aqueous solution of inert gelatin, an aqueous solution of sodium chloride and an aqueous solution of silver nitrate. At 50 ° C. so that the pAg becomes 7.0 and added by the double jet method for 60 minutes to prepare cubic silver chloride grains having an average grain size of 0.5 μm and monodispersity S = 0.14 as a red sensitizing dye (IV- 7) emulsion sensitized with red and cyan coupler (C-5) and 2,5
-Emulsion dispersion prepared by dissolving di-t-octylhydroquinone in dioctyl phthalate and a 3% aqueous solution of the dye shown in Table 2 were applied.

6th layer ... 3rd intermediate layer The following ultraviolet absorber (UV-1) and 2,5-di-t-octylhydroquinone were dissolved in dioctylphthalate to form an emulsion dispersion, which was applied.

Seventh layer ... Protective layer Mainly coated with gelatin and a hardener shown in Table 2.

The amounts of the main components (mg amount per 100 cm ² ) of each layer are shown in Table 1.

H-1 was dissolved in methyl alcohol and H-2 was dissolved in acetone and added. A total of 14 types of samples created in this way (sample numbers 1 to 14)
The performance was evaluated by the method described below, and the results are summarized in Table 3.

(1) Sensitivity After optical wedge exposure of the sample, the reference processing steps (A) and (B) for sample numbers 1 to 4 and the sample numbers 5 to 14 for
After performing the standard processing step (B), the red density of the obtained image was measured by a Sakura color densitometer PDA-60, and the relative sensitivity was determined by setting the sensitivity of Sample 2 to 100. Sample number 1-4
In the standard processing step (B), a low-sensitivity and soft-tone image was obtained and there was no suitability for rapid processing, and the standard processing step (A) was used for the subsequent evaluation of sample numbers 1 to 4.

Standard processing step <A> (processing temperature and processing time) [1] Color development 38 ° C 3 minutes 30 seconds [2] Bleach fixing 33 ° C 1 minute 30 seconds [3] Washing treatment 25-30 ° C 3 minutes [4] Drying 75-80 ℃ Approx. 2 minutes Processing solution composition (Color development tank solution) Benzyl alcohol 15 ml Erylene glycol 15 ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 5.5 g Optical brightener (4,4′-diaminostil benzsulfonic acid derivative) 1.0 g Potassium hydroxide 2.0g Add water to make the total amount 1 and adjust to pH 10.20.

(Bleaching and fixing tank liquid) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to pH 7.1 with potassium carbonate or glacial acetic acid. , And add water to bring the total volume to 1.

Standard processing step <B> (processing temperature and processing time) [1] Color development 35 ° C 50 seconds [2] to [4] Same as standard processing step <A> Color development tank liquid composition Ethylene glycol 10ml N, N'- Diethylhydroxylamine 2ml Potassium chloride 2g N-ethyl-N-β-sulfonamidoethyl-3-methyl-4-amino-aniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate 30g Adenine 0.002g Pure water was added to 1 and Adjust to pH = 10.08.

(2) Fog Each sample was subjected to standard treatment without being exposed, and the red density was measured with a Sakura color densitometer PDA-60.

(3) Desensitization with time Relative sensitivity S of sample (A) and fresh comparative sample (B) stored at 25 ° C and 60% relative humidity for 3 months
A and SB were determined by the method shown in (1) Sensitivity.

(4) Fog over time Fog of a sample produced in the same manner as for desensitization over time was determined by the method shown in (2) Fog.

(5) Infrared sensor fog Sharp Grease infrared light emitting diode GL-350 (gallium-arsenic type) 5 mm away from the light source of the sample, the sample was exposed for 5 minutes, and the exposed sample was subjected to standard treatment, and a Gretag D-122 type densitometer Was used to measure the cyan density.

As is clear from the results shown in Table 3, in Samples 1 to 4 having a low silver chloride content of silver halide, not only when the standard processing step (B) which is a rapid processing was performed,
Even when the general standard process (A) is performed, desired photographic characteristics, that is, high productivity, high yield and high image quality cannot be obtained.

Among the samples in which the silver chloride content of silver halide is 100 mol%, Samples 10 and 11 using the hardener other than the present invention exhibit large fog and fog over time. Further, in Samples 12, 13 and 14 using the dyes other than the present invention, the desensitization with time is large and the yield is greatly reduced.

On the other hand, in Samples 5 to 9 according to the present invention,
It satisfies all performances in terms of high productivity, high yield, high image quality, etc.

Example 2 In Example 1, the yellow coupler used in the first layer was (Y-35) and the magenta coupler used in the third layer was (m-
3) and the amount of silver was 4 mg per 100 cm ² , the cyan coupler used in the fifth layer was replaced by (C-6), and the red sensitizing dyes were replaced for sample numbers 23 and 24. Is the following antifoggant per mol of silver halide
10 ^-3 mol was added to prepare 14 kinds of samples shown in Table-4,
All the obtained samples were evaluated in the same manner as in Example 1 using the standard treatment step (B), and the results are summarized in Table-5.

As is clear from the results shown in Table 3, even if the yellow coupler used in the first layer, the magenta coupler used in the third layer and the cyan coupler used in the fifth layer were changed, the sample according to the present invention was prepared as in Example 1. The effect of the present invention that can be confirmed in the above was obtained.

Even if the red sensitizing dye was changed, the effect of the present invention was similarly exhibited.

On the other hand, in the samples other than the present invention, even if an antifoggant is used to suppress fog, the effect of suppressing fog over time is small, and the sensitivity is significantly lowered.

Continuation of the front page (56) Reference JP 61-47941 (JP, A) JP 60-162246 (JP, A) JP 59-210437 (JP, A) JP 60-221747 (JP , A) JP-A-49-5125 (JP, A) JP-A-51-77327 (JP, A)

Claims (5)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
In a silver halide color photographic light-sensitive material having a green light-sensitive silver halide emulsion layer and a red light-sensitive silver halide emulsion layer, at least the red light-sensitive silver halide emulsion layer has a silver chloride content of 80 mol% or more. A silver halide grain containing a silver halide grain and hardened with a compound represented by the following general formula [I] and / or a compound represented by the following general formula [II]. A silver halide color photographic light-sensitive material characterized in that the light-sensitive material contains a water-soluble bispyrazolone pentamethine oxonol dye having an absorption maximum wavelength of 660 nm to 680 nm in a gelatin film. General formula [I] In the formula, R ₁ is chlorine atom, hydroxy group, alkyl group, alkoxy group, alkylthio group, -OM group (M represents a monovalent metal atom), -NR'R "or -NHCOR (R ', R".
And R each represent a hydrogen atom, an alkyl group or an aryl group), and R ₂ has the same meaning as R ₁ excluding a chlorine atom. General formula [II] In the formula, R ₃ and R ₄ are each a chlorine atom, a hydroxy group,
An alkyl group, an alkoxy group or an -OM group (M represents a monovalent metal atom), -Q- and -Q'- each represent a -O-, -S- or -NH- linking group, L represents an alkylene group or an arylene group. l and m each represent 0 or 1. 2. The silver halide grains having a silver chloride content of 80 mol% or more contained in the red light-sensitive silver halide emulsion layer are monodisperse silver halide grains. A silver halide color photographic light-sensitive material according to item 1. 3. The red-sensitive silver halide emulsion layer according to claim 1, wherein the silver halide emulsion layer contains silver halide grains having a silver chloride content of 90 mol% or more. Silver halide color photographic light-sensitive material. 4. A water-soluble bispyrazolone pentamethine oxonol dye having a spectral absorption maximum in the wavelength range of 660 to 680 nm in a gelatin film is a compound represented by the following general formula [III]. Claim 1,
A silver halide color photographic light-sensitive material according to item 2 or 3. General formula [III] In the formula, R ₅ and R ₆ each represent —CN or —COOR ₉ , and R ₉ represents an alkyl group or an aryl group. L represents a methine group. R ₇ and R ₈ each represent an aliphatic group, an aromatic group or a heterocyclic group. 5. A silver halide grain having a silver chloride content of 80 mol% or more contained in the red light-sensitive silver halide emulsion layer is prepared from a sensitizing dye represented by the following general formula [IV] or [V]. The silver halide color photographic light-sensitive material according to any one of claims 1 to 4, which is color-sensitized with at least one sensitizing dye selected. General formula [IV] General formula [V] In the formula, R ₁₀ and R ₁₁ each represent an alkyl group or an aryl group, and L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each represent a methine group. Z ₁ and Z ₂ each represent an atom or a group of atoms necessary for completing an oxazole ring, a thiazole ring or a selenazole ring. Z ₃ represents a hydrocarbon atom group necessary for forming a 6-membered ring. X represents an acid anion. m ₁ , m ₂ , n and l ₁ each represent 0 or 1. However, l is 0 when the compound forms an inner salt.