JPS62250438A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make a silver halide photographic sensitive material suitable for rapid processing as well to attain high sensitivity and low fog by hardening a silver halide emulsion layer contg. silver halide particles having >=80mol% silver chloride content with a specified compound and by using a water soluble bispyrazolonepentamethioneoxonol dye having the absorption maximum wavelength at 660-680nm. CONSTITUTION:The red-sensitive silver halide emulsion layer of a silver halide photographic sensitive material is hardened with a compound represented by formula I and/or a compound represented by formula II. The emulsion layer contains silver halide particles having >=80mol% silver chloride content and the sensitive material contains a water soluble bispyrazolonepentamethineoxonol dye having the absorption maximum wavelength in a gelatin film at 660-680nm. The hardening agent is dissolved in water or alcohol and added by 0.5-100mg, preferably 2-50mg per 1g coated gelatin. The absorption maximum wavelength of the dye is determined by measuring the spectral absorption maximum in the gelatin film. In case where the absorption maximum wavelength is <660nm or >680nm, considerable desensitization is caused with the lapse of time. In the formula I, R1 is Cl, hydroxy, alkyl, alkoxy, alkylthio, -OM (M is a univalent metallic atom), -NR'R'' or -NHCOR''' (each of R', R'' and R''' is H, alkyl or aryl) and R1 is a group represented by R1 other than Cl. In the formula II, each of R3 and R4 is Cl or the like, each of Q and Q' is a combining group such as -O-, L is alkylene or the like, l=0 or 1 and m=0 or 1.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically to a silver halide photographic material that has high sensitivity and low capri, and can be used quickly with little desensitization or increase in capri even with aging of the sample. This invention relates to silver halide color photographic materials suitable for processing.

[Background of the Invention] Generally, silver halide color photographic light-sensitive materials consist of three types of silver halide photographic materials that are selectively spectral sensitized to have sensitivity to blue light, green light, and red light on a support. An emulsion layer is applied. 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 there is a layer between the blue-sensitive emulsion layer and the green-sensitive emulsion layer. A bleachable yellow filter layer is provided to absorb the blue light transmitted through the blue-sensitive emulsion layer. Generally speaking, each emulsion layer is provided with other intermediate layers for various special purposes, and a protective layer as the outermost layer. In addition, for example, in exposed materials for color photographic paper, the layers are generally coated in the order of red-sensitive emulsion layer, green-sensitive emulsion layer, and blue-sensitive emulsion layer from the side to be exposed, and each layer has a special coating, similar to that in color negative photosensitive materials. For this purpose, intermediate layers including an ultraviolet absorbing layer, protective layers, etc. are provided. It is also known that each of these emulsion layers may be provided in a different arrangement from the above, and each emulsion layer may be provided with a photosensitive layer consisting of two layers that are sensitive to substantially the same wavelength range for each color light. It is also known to use emulsion layers. In these silver halide photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by the reaction of the dye with the dye-forming coupler. In this method, phenolic or naphtholic cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanoacetyl couplers are used to form cyan, magenta and yellow dye images, respectively. Magenta couplers and acylacetamide-based or benzoylmethane-based yellow couplers are used. These dye-forming couplers are contained in the light-sensitive photographic emulsion layer or in the developer solution. The present invention relates to a silver halide photographic material in which these couplers are preliminarily contained in an emulsion layer and rendered non-diffusive.

Incidentally, in recent years, various measures have been taken to speed up color development. As one method, it is known to use a color development accelerator when developing an exposed silver halide photographic light-sensitive material using an aromatic primary amine color developing agent. For example, as such color development accelerators, U.S. Pat.
, No. 038,075, No. 4,119,462, British Patent No. 1,430,998, No. 1,455,413, Japanese Patent Application Publication No. 53-15831, No. 55-62450, No. 5
No. 5-62451, No. 55-62452, No. 55-6
No. 2453, No. 51-12422, Special Publication No. 51-12
Compounds described in No. 422, No. 55-49728, etc. have been investigated, but most of these compounds have insufficient development accelerating effects, and among these compounds, only a few compounds exhibit sufficient development accelerating effects. However, it has the disadvantage of often producing fog, making it impractical.

In addition, various penetrants have been studied to promote the penetration of color developing agents into silver halide photosensitive materials, and among these, a method of accelerating color development by adding benzyl alcohol to a color developer is widely used. It is being

However, this method is somewhat difficult in terms of rapid processing because, for example, at a processing temperature of 33° C., a sufficiently high color density cannot be obtained unless the processing is carried out for 3 minutes or more. In addition to the processing temperature, 1) H? A method of developing color by raising the DH to 11 degrees has also been proposed, but for example, increasing the DH to 10 degrees.
If the temperature is above 5LX, the oxidation of the color developing agent is significantly accelerated, and the lack of a suitable buffer solution makes the color developing agent susceptible to pH changes, making it difficult to obtain stable photographic performance. , there is a problem that the processing time becomes highly dependent.

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

However, this method has the disadvantage that the raw storage stability of the silver halide photographic light-sensitive material is poor, and fog is likely to occur before use, and furthermore, fog is likely to occur during color development processing.

Furthermore, in order to inactivate the amine moiety of the color developing agent, there is a method of incorporating the color developing agent into, for example, a Schiff salt, as described in US Pat. No. 3,342,559, for example.
Research Disclosure, 1976 No.
15159. However, in these methods, color development does not start until after the color developing agent has been alkaline-hydrolyzed, so that the problem is that color development is rather delayed.

Furthermore, JP-A-56-64339 describes a method of adding 1-aryl-3-pyrazolidone having a specific structure to a silver halide color photographic light-sensitive material, and JP-A-57-64339 describes
No. 144547, No. 58-50532, No. 58-50
No. 533, No. 58-50534, No. 58-50535
No. 58-50536 discloses that 1-arylpyrazolidones are added to a silver halide color photographic light-sensitive material, and processing is performed within a relatively short developing time.

However, the techniques described in these publications are not necessarily satisfactory in terms of obtaining dye images with sufficient color development speed and high color density, and there is still room for improvement. .

In addition, in terms of other photographic performance, it is often accompanied by negative effects such as decreased sensitivity, softened contrast, and increased fog, so it is difficult to achieve both sufficient speed of color development and high quality in other photographic performance. There is also a problem.

By the way, silver halides used in silver halide photographic materials generally include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. used. Silver chlorobromide or silver chloride containing 80 mol % or more of these silver oxides has excellent suitability for rapid processing, and research on these can be found in, for example, JP-A No. 55-1358324 and JP-A No. 58-1.
No. 25,012, JP-A No. 60-222.844, and British Patent No. 149,573. However, as described in the above patent, silver halide containing 80 mol% or more of silver chloride has low sensitivity and high capri, and furthermore, as the sample ages, it tends to desensitize and increase capri, and especially for capri, Known anti-capri agents and stabilizers such as tetrazaindenes, mercaptotriazoles, mercaptoimidazoles, catechols, and resorcinols have little effect, and excessive use causes significant desensitization.

On the other hand, silver halide photographic materials! 31 (hereinafter referred to as photo@materials), dyes are contained in photographic forest materials for the purpose of absorbing light of specific wavelengths for filters, anti-halation, anti-irradiation, or to adjust the sensitivity of photographic emulsions. It is common practice to color the hydrophilic colloid layer with a dye.

In addition, 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 the back surface of the support. It is often done to prevent halation by absorbing reflected light, or to prevent irradiation by coloring the emulsion layer to absorb harmful reflected light or scattered light from silver halide grains, etc. ing.

Dyes used for such purposes must have good absorption spectrum characteristics depending on the purpose of use, be completely decolorized in photographic solutions, be easily eluted from photographic materials, and be free from residual color due to dyes after processing. There is no contamination, there is no adverse effect on the photographic emulsion such as capri, desensitization, etc., there is no diffusion from the dyed layer to other layers, and there is
Alternatively, it must satisfy conditions such as excellent stability over time in photographic materials and no discoloration or fading.

To date, many efforts have been made and a large number of dyes have been proposed with the aim of finding dyes that satisfy the above conditions. For example, British Patent No. 506,385
U.S. Pat. No. 3,247,127, Japanese Patent Publication No. 39-22069f! Publication and Special Publication Sho 43-1316
oxonol dyes described in U.S. Pat. No. 8, etc., styryl dyes as typified by U.S. Pat. Cyanine dyes represented by 486@, and even U.S. Patent No. 2,865,75
There are anthraquinone dyes represented by No. 2.

Among these dyes, the bisbentamedine oxonol dye, which acts on the red-sensitive emulsion layer, has a spectral absorption characteristic of
On the other hand, it has the ability to suppress photosensitive fog (hereinafter referred to as infrared sensor fog) caused by infrared sensitive sensors, which have recently been increasingly applied to production processes and automated processes such as photosensitive material printers and processing equipment. is lacking.

The emission wavelength of the infrared sensitive sensor 1 differs in various ranges depending on the light emitter used, but for example, a typical Q
In the a-AS liquid phase epitaxial type infrared light emitting diode, the same type using 900 to 950011 Si has a wavelength of about 1140 tv, and the same type using Ge has a wavelength of about 1880 nm.

On the other hand, the binder used in color photosensitive materials for printing mostly involves gelatin, and the hardening agent for the binder is used as a binder.

Desired properties of the hardening agent are that it has a rapid hardening effect, that it does not have any adverse effects on silver halide such as capri, and that it does not cause problems in labor hygiene or environmental pollution.
It is water soluble, easy to synthesize, and low cost.

For this purpose, studies were conducted on hardening agents such as vinyl sulfone, ethyleneimine, epoxy, N-methylol, and chlorotriazine.
1-Ryazine hardeners as described in JP-A-48-19220, JP-A-51-78788, JP-A-52-128130, JP-A-52-130326 and JP-A-5G-1043 are It satisfies most of the characteristics and has excellent characteristics.

However, this chlorotriazine-based l1il! Filming agents act on silver halide to reduce sensitivity, and furthermore, as the sample ages, the sensitivity decreases, which is a major drawback that goes against the recent high productivity.

[Objective of the Invention 1] The present invention was made in view of the above-mentioned circumstances, and as a result of extensive research into dyes and hardeners, a red-sensitive resin containing silver chloride of 80 mol% or more [1] To the silver germide grains,
By combining special dyes and specific hardeners,
It is an object of the present invention to provide a silver halide color photographic material that is highly sensitive, has low fog, is suitable for rapid processing, and satisfies recent demands for high productivity.

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

A second object of the present invention is to provide a silver halide photographic material that exhibits less desensitization and less increase in fog over time.

The purpose of ff13 of the present invention is to produce a silver halide photosensitive material F1 with less infrared bottle length and force blur.

[Structure 1 of the invention] The above-mentioned object of the present invention is to form a gate-sensitive silver emulsion layer d3, a green-sensitive silver emulsion layer d3, and a red-sensitive silver genide emulsion layer d3 on a support. In the silver emulsion having a silver emulsion, 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 a compound represented by the following general formula [II], lii! The silver halide photographic light-sensitive material has a maximum absorption wavelength in the gelatin film of GGOrv~1380nl.
This is achieved using a silver halide photographic material containing a water-soluble bisvirazolone pentamedine oxonol dye.

General formula [I] In the formula, R1 is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, a -0M group (M represents a monovalent gold atom), -NR'R'' or - N
HCOR"'(R',R" and R each represent a hydrogen atom, an alkyl group or an aryl group), and R2 has the same meaning as <R+ except for the chlorine atom.

General formula [I[] In the formula, R31Jj J: Bi! (1 represents J! elementary atom, hydroxy group, alkyl group, alkoxylll& or -OMJJ (M represents a monovalent metal atom), respectively, -Q- and -Q'- respectively -〇-1-S- or -N 1-1- represents a linking group, L represents an alkylene group or an arylene group, and l and steel each represent 0 or 1.

[Specific Structure of the Invention] In the present invention, the silver halide grains contained in at least the red-sensitive silver halide emulsion layer (hereinafter referred to as silver halide grains according to the present invention) are 80 mol% or more. It has a silver chloride content of . 0-f preferably 90 mol%
It has a silver chloride content of the above. Further, the content of silver iodide is 1 mol% or less, preferably 0.5 mol% or less. More preferred 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 in combination with silver halide grains having a silver chloride content of less than 80 mol %.

Further, the 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. at least 50% by weight of, preferably at least 751ij? t%.

The composition of the silver halide grains 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. Furthermore, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

Although the grain size of the silver halide grains according to the present invention is not particularly limited,
4Ii1 is preferably in the range of 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm. The particle diameter can be measured by various methods commonly used in the technical field.

A typical method is Loveland's particle size analysis method.
Eight, S, T.

M, Symposium on Light Microscopy 1
955, pp. 94-122, and Chapter 2 of [Theory of Photographic Process], co-authored by Mies and James, 3rd edition, published by Macmillan Publishing Co., Ltd. (1966). The particle size 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 expressed fairly accurately as either diameter or projected area.

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

Here, ``1'' represents the grain size of the particle steel, and nl represents its number.

The grain size here refers to the diameter in the case of spherical silver halide grains, and the diameter when the projection is converted into a circular image of the same area in the case of grains with shapes other than cubic or spherical. represents.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent No. 4.183.75'6, U.S. Pat.
No. 25,666, JP-A No. 55-26589, JP-A No. 5
Specifications such as No. 5-42737, The Journal of Photographic Science (J, Photo
gr, 5ci), 21.

39 (1973), etc., by the method described in the literature such as
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can also be prepared and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of 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 according to the present invention and the silver halide grains used in the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide rough emulsion layer, that is, the silver halide grains used in the present invention, are produced by an acidic method. It may be obtained by either the ammonia method or the ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

Further, the method of reacting the soluble silver salt with the soluble halogen salt may be any of the forward mixing method, back mixing method, simultaneous mixing method, and combinations thereof, but those obtained by the simultaneous mixing method are preferred. Further, as a form of the simultaneous 44 method, the pAg-con] rolled double jet method described in Japanese Patent Application Laid-Open No. 54-48521 and the like can also be used.

Furthermore, if necessary, a silver halide solvent such as dioether,
Alternatively, a crystal habit control 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 may be prepared from cadmium salts, zinc salts, lead salts, thallium salts, iridium cum salts or complex salts, rhodium salts or complex salts, Metal ions can be added to the inside of the particles and/or on the surface of the particles using iron salts or complex salts, and by placing them in an appropriate reducing atmosphere, reduction sensitization can be achieved inside the particles and/or on the surface of the particles. It is also possible to add a nucleus.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the emulsion of the present invention may be grains in which a latent image is mainly formed on the surface,
Alternatively, the particles may be formed mainly inside the particles. Preferably, the particles are particles in which the image ii is mainly formed on the surface.

The emulsion of the present invention is chemically sensitized by conventional methods.

Namely, sulfur sensitization using a sulfur-containing compound capable of reacting with silver ions or activated gelatin, selenium sensitization using a selenium compound, reduction sensitization using a reducing substance, and gold or other depressant metal compounds. Metal sensitization methods can be used alone or in combination.

The silver halide emulsion of the present invention can be spectrally sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. Sensitizing dyes may be used singly or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide emulsions are used during and/or at the end of chemical ripening, and/or after the end of chemical ripening. Compounds known in the photographic industry as antifoggants or stabilizers can be added prior to coating.

Next, a compound represented by the general formula [I] and a compound represented by the general formula [I]
[The compound represented by 1 will be explained.

General formula [I] z In the formula, R1 is a chlorine atom, hydroxy group, alkyl group, alkoxy group, alkylthio group, -0M group (M represents a monovalent metal atom 1), -NR'R" or - NHCOR
"'(R',11" Jj and R"' each represent a hydrogen atom, an alkyl group or an aryl group), and R2 is 1 (synonymous with 1) except for the chlorine atom.

General formula [1] In the formula, R3 and R4 are each a chlorine atom, hydroxy group, alkyl group, alkoxy group or -OM group (M is 1
represents a valent metal atom), -Q- and -Q'-
each represents a linking group of -0-1-S- or -NH-, and L represents an alkylene group or an arylene group. l and m each represent 0 or 1.

R of the hardening agent represented by the general formula [I] according to the present invention
Examples of the alkyl group represented by 1 and R2 include methyl group, edyl group, butyl group, etc. Specific examples include -
N112, -NHCH3, -N H02R5, etc., -N
This is a concrete example of HCOR. Furthermore, the expression 1 for R* and R2
M in the -0M group is, for example, a sodium atom, a potassium atom, or the like.

Regarding the chlorotriazine hardeners represented by the general formula [I], US Pat.
No. 9607, JP-A-48-19220, JP-A No. 51-78
No. 788, No. 52-60612, Jili 52-
No. 128130, No. 52-130326, No. 56-
No. 1043, which can be used in accordance with the above criteria.

Next, the alkyl group represented by Ra and R4 in the general formula [I[] 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., and -0M The group M is, for example, a sodium atom,
Potassium atoms, etc.

Further, the alkylene group represented by L is, for example, -CH2-1-
(CH2)2-1-(CH2)a group, etc., and the arylene group is, for example, D-10- or l-phenylene group.

The chlorotriazine hardener represented by the general formula [1] is described in Canadian Patent Nos. 895 and 808, Japanese Patent Publication No. 58-33542, Japanese Patent Application Laid-Open No. 57-40244, etc., and based on the above standards, can be selected and used.

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

The method of adding the hardener used in the present invention is to dissolve the hardener of the present invention in water or alcohol (e.g., methyl alcohol, ethyl alcohol, etc.) and add 0.5 to 10 GIQ, preferably 2 to 50 GIQ, per 1 g of coated gelatin. -9 may be added. The addition method may be either a batch method or an in-line method.

The hardening agent represented by the general formula [I] or [I] according to the present invention is disclosed in U.S. Patent No. 3,490,911 and West German Patent No. 2.7.
Vinyl sulfone hardeners described in No. 49,260, U.S. Pat. Nos. 2,950,197 and 2,804,404,
No. 2,983.611, j2i13,271,175
No., Special Publication No. 46-40898, Japanese Unexamined Patent Publication No. 50-9131
Aldehyde hardeners and aziridine hardeners described in No. 5, or U.S. Patent No. 3.04γ1394, West German Patent No. 1,085,663, British Patent No. 1.033
, No. 518, Japanese Patent Publication No. 48-35495, etc., and combination use with vinyl sulfone hardeners is particularly preferred. When the hardener of the present invention and the vinyl sulfone hardener are combined, the ratio is 1:0.
．． 2-1:5.0 (1 m) is preferable.

Typical specific examples of compounds represented by the general formula [I] or [I[] are listed below, but the present invention is of course not limited thereto.

-41 Folded axis - Congruent with East Rui indicated by l: (1-5)
(l-6) (1-9
) (1-1(>)(1-11
) (I-12) One insect! Takeshi [H-I play with illusions (Compound: ([-1) CI-3) (ff-4) (I[-5) (It-6) (I[-7) (U-8 ) (II-9) (It-10) The bispyrazolone pentamethine oxonol dye according to the present invention can be selected by measuring the spectral absorption density in a gelatin film by the method shown below.

That is, the dye was dissolved in a 5% aqueous solution of alkali-treated ossein gelatin to a concentration of 0.01%, and then the gelatin coating amount was 50/1" and the dye coating amount was 10 μQ/f.
After coating and drying on a transparent support so that Dyes with a maximum absorption wavelength of less than 66 On- and dyes with a maximum absorption wavelength of 6B0 nm or more experience significant desensitization over time.

Next, the general formula [111
The dye represented by will be explained.

General formula [111] In the formula, R5 and R6 are each -CN or -COOR
s and R9 represents an alkyl group or an aryl group. L represents a methine group. Particularly preferably R5 and R
6 is -CN.

R7 and R8 each represent an aliphatic group, an aromatic group or a heterocyclic group.

In the above general formula [111], R9 of one COORs represented by R5 and R6 represents an alkyl group or an aryl group, and the alkyl group and aryl group include those having a substituent. Examples of the alkyl group include methyl, ethyl, oxyethyl, cyanoethyl, hydroxyethoxyethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl,
Examples include dodecyl, pentadecyl, octadecyl, benzyl and the like. Furthermore, examples of the aryl group include substituted and unsubstituted ones such as phenyl, tolyl, ethylphenyl, chlorophenyl, methoxyphenyl, and naphthyl.

R7 and R8 each represent an aliphatic group, an aromatic group, or a heterocyclic group, and among these, the aliphatic group includes alkyl N (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, octyl group, dodecyl group, etc.), cycloalkyl group (eg, cyclohexyl group, etc.), and alkenyl M (eg, butenyl group, etc.). Furthermore, typical aromatic groups include aryl groups such as phenyl and naphthyl groups. Furthermore, as a heterocyclic group,
For example, representative examples include a benzthiazolyl group and a penzooxazolyl group.

The aliphatic group, aromatic group, and heterocyclic group represented by R7 and R8 further include a hydroxy group, an amino group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.),
Alkoxy group (e.g. methoxy group, ethoxy group, etc.),
It may be substituted with a carboxy group, a carbamoyl group, a sulfo group, a sulfamoyl group, an aryl group (eg, phenyl group, 4-sulfophenyl group, etc.), an aryloxy N (eg, phenoxy group, 4-sulfophenoxy group, etc.), or the like. In addition, an aryl group is an alkyl group having 1 to 4 carbon atoms (
For example, it may be substituted with a methyl group, an ethyl group, etc.).

Further, examples of the aryl group represented by R7 and R8 having a sulfo group include a 4-sulfophenyl group, a 3-
Sulfophenyl group, 2-methyl-4-sulfophenyl group, 2-O-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 o-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-naphthyl group group, 6,8-disulfo-β
-naphthyl group and the like. Furthermore, the R3
Examples where the heterocyclic group of and R+ is substituted with a sulfo group include 2-(6-sulfo)benzthiazolyl group, 2-
(6-sulfo)benzoxazolyl group and the like can be mentioned.

The sulfo group may also be bonded to an aryl group via a divalent organic group, such as 4-(4-sulfophenoxy)phenyl group, 4-(2-sulfoethyl)phenyl group, 3-(sulfophenoxy)phenyl group, methylamino)phenyl group, 4-(
2-sulfoethoxy)phenyl group may be mentioned.

Further, examples in which the aryl group represented by R7 and R8 are substituted with a carboxy group include 4-carboxyphenyl, 3.5-dicarboxyphenyl, and 3.5-disulfophenyl-3-carboxy-4-human O Kissy 5-
Examples include sulfophenyl.

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

Among R5 and R6, -CN group is preferred. Of R7 and R8, preferably an aromatic group, particularly preferably a 4-sulfophenyl group, 2.
It is a 5-di-sulfophenyl group.

Typical specific examples of the dye of the present invention represented by the general formula [I[1] are shown below, but the dye of the present invention is not limited thereto.

(IL-1) (X-2) ('jL-3) N Fi Cl”i 28:i(J 3 Na
H shi Fl 2 b (J 3 N i(
(5-noon) (IL-51 (m-8) CH.

■ (] [−’?) C,H.

(IIL-to) (Summer-11) C, I-11 (X-1, S> CH.

(X-1s) The dye represented by the general formula [111] is a 3-cyano-5-pyrazolone compound represented by the following general formula [I[[-AI] and the following general formula [I[1- 8], [I[[-C],
It can be synthesized by reacting a compound represented by [I[[-DI or [I[[-El] in the presence of a base.

General formula [1[[-AI General formula [I[[-Bl General formula [1[[-G] HC(OR')3 General formula [111-DI General formula [[-El] In the formula, R3, L and n represents the same meaning as in the general formula [1[[], and G is a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom), or a -specific IIl group, a trifluoromethyl group, an ethoxy Represents a carbonyl group. X is an anion (e.g. chloride,
Bromide, iodide, barchlorate, p-1~
luensulfonate, methylsulfonate, ethylsulfonate, etc.), and m represents 0 or 1.

R' represents a medyl group or an ethyl group.

The bases to be present include pyridine, piperidine,
Triethylamine, triethanolamine, morpholine, ammonia, etc. are used.

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

The reaction is suitably carried out at a temperature from 0°C to the boiling point of the solvent used.
The 3-cyano-5-pyrazolone compound represented by -AI has the general formula [I[[-Bl, [I[[-C], [1[1-DI
Alternatively, it is appropriate to use approximately twice the mole of the compound represented by [111-El].

Further, the 3-cyano-5-pyrazolone compound represented by the general formula [■-Δ] can be synthesized using the production method described in British Patent No. 585.780.

Synthesis of the oxonol dye of the present invention will be specifically explained below by showing synthesis examples.

Synthesis Example 1 (Synthesis of Exemplary Dye (III-1)) 1-(4'
-sulfophenyl)-3-cyano-5-pyrazolone 10
．． 647 and glutacondialdehyde cyanyl hydrochloride5.
7 g of the mixture were placed in dimethyl formaldehyde 100112, and 6.1 g of triethylamine was added thereto, followed by stirring at room temperature for 4 hours. Next, 5.9 g of potassium acetate dissolved in 150 tQ of methanol was added and stirred. The precipitated dye crystals were collected by filtration, washed with acetone, then methanol, and dried to obtain 9.1 g of dye. The aqueous solution of this dye had a λmax of 645 nm.

Further exemplary dyes I[I-6 and I[[-8 to I[[-
No. 16 is manufactured according to the method described in JP-A No. 48-62826. Representative examples are shown below.

Synthesis @3 (Synthesis of dye ■-13) A green-blue crystalline dye was obtained in the same manner as in Synthesis Example 2 using 1-(4'-sulfophenyltoxy-5-pyrazolone and glutacondialdehyde cyanyl hydrochloride) An aqueous solution of 1/200,000 polymer parts of this dye exhibited a blue color, λmax 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 [1[] may be contained in any layer of the light-sensitive emulsion layer or non-light-sensitive layer of the silver halide photographic light-sensitive material. is preferably used in the red-sensitive silver halide emulsion layer of the present invention or its adjacent non-light-sensitive layer.

Furthermore, depending on the purpose of use, two or more types of dyes according to the present invention may be used, or they may be used in combination with other dyes. In order to incorporate the dye according to the present invention into a silver halide photographic emulsion layer or other hydrophilic colloid layer, the dye or an organic or inorganic alkali salt of the dye is generally added to an aqueous solution or an organic solvent (such as alcohol). , glycols, cellosolves, dimethyl formaldehyde,
dibutyl phthalate, tricresyl phosphate, etc.)
The dye can be incorporated into the silver halide photographic light-sensitive material by dissolving it in a silver halide photographic material, emulsifying and dispersing it if necessary, and adding it to a coating solution for coating. The content of these dyes varies depending on the purpose of use, but is generally 0.01 to 0.5 u/
It is applied and used so that df1 is preferably 0.03 to 0.2 mg/d12.

When the dye according to the present invention is used in combination with other dyes other than the present invention, particularly preferred dyes include the following general formula [VI] shown in U.S. Patent No. 2.865.752 etc.
It is an anthraquinone dye represented by

General formula [VI] In general formula [VI], R+, R4, Rs and R8 each represent a hydrogen atom, a hydroxy group, an -OR group or an aryl group, and R' and R'' are a hydrogen atom or at least one
R2, R3, R6 and R7 each represent a hydrogen atom, a carboxylic acid group, a sulfonic acid group or at least one carboxylic acid group or sulfonic acid group; represents an alkyl group or an aryl group.

The alkyl group represented by R in the -OR group represented by R1, R4, Rs and R8 in the general formula [VI] is, for example, a methyl group,
It is an ethyl group or a butyl group, and the aryl group represented by R is, for example, a phenyl group.

Further, the alkyl group represented by R' and R'' in -NR'R''l and having at least one sulfonic acid group or carboxylic acid group is, for example, -OH2SOaH.

-(CH2)2 SO3H, -CH2C0OH.

-(CH2)2C0OH or its sodium salt, potassium salt or ammonium salt. Also, Ru.

Further, the alkyl group or aryl group having at least one carboxylic acid group or sulfonic acid group represented by R-2, R3, R6 and R7 can be the same as those represented by R' and R''.

The compound represented by the general formula [V[] is usually used dissolved in water or alcohol, and the amount added is 1 to 1100 II1/f, preferably 5 to 50 I1/f, in the light-sensitive material.
It is added so that it becomes I1g/f.

Further, when used in combination with the dye of the present invention, the ratio of the dye of the present invention to the above-mentioned anthraquinone dye is preferably 1:0.5 to 1:4 by weight.

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

[W-1] H ['/I -2] A [VI -3] [VI -41 [VI-51 [VI-61 Bar OHONHCHzSOsNa [W -7] [W-8] [Vl -9] (JM ONHCHzCH2SOsNa[VI-10
1 [VI-111 [VI-121 Na Os S Ht CN ON HCH2
S Os Na [■-131 CH.

[VI-14] [VI-151 ○Cl(3 [Vl-161 [■-171] [VI-181 OHONM ti25su3NIL [91-191;
Or [The sensitizing dye represented by Vl will be explained.

General formula [IV] General formula [11r] In the formula, R5 and R6 each represent an alkyl group or an aryl group, Ll, L2, L3, L+ and L5
represents a methine group. zl and z2 each represent an atom or atomic group necessary to complete the oxazole ring, thiazole ring or selenazole ring. z3 represents a group of hydrocarbon atoms necessary to form a 6-membered ring. X (9 represents an acid anion. ml, L12, n and 11 each represent O or 1. However, when the compound forms an inner salt, 2 is 0.

In general formulas [IV] and [VI, R5 and R6
The alkyl group represented by may be branched or have an unsaturated bond. More preferably, the number of carbon atoms is 10 or less, such as sulfo, aryl,
Carboxy, amine (-class, secondary, tertiary), alkoxy, aryloxy, hydroxy, alkoxycarbonyl,
It may have an atom or substituent such as acyloxy or halogen. Specific examples include methyl group, ethyl group, sulfobutyl group, benzyl group, phenethyl group, carboxymethyl group, dimethylaminobutyl 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-
Carboxyphenethylxycarbanylmethyl group, pivaloylpropyl group, propionylethyl group, anisyl group,
These include acetoxyethyl group, benzoyloxyprobyl group, chloroethyl group, N-ethylaminocarbonylprobyl group, allyl group, 2-butynyl group, cyanoethyl group, and the like.

Furthermore, the aryl group represented by R5 and R6 is, for example, a phenyl group, a carboxyphenyl group, a sulfophenyl group, or the like.

When the methine group represented by Ll, L2, and L3 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 (
For example, methyl group, ethyl group, carboxymethyl group, benzyl group), alkoxy group (e.g. methoxy group, ethoxy group) and aryl group (e.g. phenyl group, tolyl group)
Examples include.

Specific examples of the thiazole nucleus, selenazole nucleus or oxazole nucleus completed by 71 and z2 of the general formulas [IV] and [VI 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-methylbenzothiazole,
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]thioxazole, naphtho[1,2-d]oxazole,
naphtho[2.1-d]oxazole, naphtho[2.3
-d ]oxazole and the like.

Acid anions represented by X in general formulas [IV] and [VI include, for example, chlorine ion, bromide ion, iodide ion, perchlorate ion, fluoroborate ion, o-toluenesulfonate ion, ethylsulfonate ion, Examples include nitrate ion.

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

General formula [Va] (Xe)ffi.

In the formula, Yl and Y2 each represent an oxygen atom, a sulfur atom or a selenium atom, and R10 and R++ represent a lower alkyl group.

A1, A2, B+, 82, C1, C2, Dl and B2 are each a hydrogen atom, a halogen atom, an alkyl group,
Represents an alkoxy group, phenyl group, cyano group, nitro group or alkoxycarbonyl group.

Furthermore, at least one of the combinations of A1 and B1, B1 and C1, C1 and Dl, A2, 82.82 and C2, and C2 and B2 may be condensed to form a benzene ring.

A1, A2, B1 of general formula [IVal and [Va ]
, B2, C1, C2, Dl and B2 are linear or branched lower alkyl groups having about 1 to 5 carbon atoms (for example, methyl group, ethyl group, butyl group, trifluoro The alkoxy group is a linear or branched alkyloxy group having about 1 to 5 carbon atoms (e.g. methoxy group, ethoxy group), and the halogen atom is fluorine, chlorine, bromine or iodine. The phenyl group is, for example, a phenyl group without a substituent, a hydroxyphenyl group, or a carboxyphenyl group, and the alkoxycarbonyl group is, for example, a methoxycarbonyl group or an ethoxycarbonyl group.

R5, R6, Ll, L2, L3, Shi+, L5, Xe)
, n and ILl have the same meanings as explained in the above general formulas [IV] and [V], respectively. However, it is more preferable that n is 1.

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 limited to these.r/-1 f-2 Of -3 ■-4 ShiFl 2 Shi101t (J Shitl s
Ct k'i sIV-9 ■-10 Iθ ■-11 e ■-12 ■-14 V-T-teme V''-7 1 mountain V-pi V-10 The above general formula according to the present invention The sensitizing dye represented by [IV] or [Vl may be added at any time during the emulsion manufacturing process, but it is preferably added during or after chemical ripening, and more preferably during chemical ripening. Amount added. is from 10@-7 to 10@-3 mol, preferably from 5.times.10@-6 to 5.times.10@-3 mol, per mole of silver halide.

When silver halide grains contained in a red-sensitive silver halide emulsion layer are color-sensitized using the sensitizing dye represented by the above general formula [IV] or [Vl], the sensitivity is high and there is little desensitization over time. This effect of the present invention can be further enhanced.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film, a positive film, or a color photographic paper. In particular, when a color photographic paper intended for direct viewing is used, the method of the present invention can be used. The effects of this will be effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic light-sensitive materials, in order to perform subtractive angle color reproduction, a photographic coupler is usually used.
It has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate calendar number and temperature order. It may be changed as appropriate depending on the important performance and purpose of use.

When the silver halide photographic light-sensitive material of the present invention is a multicolor light-sensitive material, the specific layer structure includes a yellow dye image-forming layer, an intermediate layer, a magenta dye of the present invention, and Particularly preferred is an arrangement of an image forming layer, an intermediate layer, a cyan dye image forming layer, an intermediate layer, and a protective layer.

As mentioned above, the red-sensitive silver halide emulsion has the general formula [IV
] or [Although it is preferable to color-sensitize with a sensitizing dye represented by Can be optically sensitized to a wavelength range. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
Silver halide emulsions are used during chemical ripening, and/or at the end of chemical ripening, and/or after the end of chemical ripening, for the purpose of preventing fog during storage or photographic processing, and/or keeping photographic performance stable. Compounds known in the photographic industry as antifoggants or stabilizers can be added prior to coating.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
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 single or copolymers can also be used.

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

A dispersion of a water-insoluble or sparingly soluble synthetic polymer (
Terrax) can be included.

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of p-phenylenediamine derivatives, aminophenol derivatives, etc.). The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler in the blue light-sensitive emulsion layer. , a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is British Patent No. 1,077.874.
No., Special Publication No. 45-40757, Japanese Patent Publication No. 47-1031
No. 47-26133, No. 48-94432, No. 50-87650, No. 51-3631, No. 52-1
No. 15219, No. 54-99433, No. 54-13
No. 3329, No. 56-30127, U.S. Patent No. 2,8
No. 75,057, No. 3.253.924, No. 3, 26
5.506, 3,408,194, 3,5
No. 51,155, No. 3,551,156, No. 3.66
No. 4.841, No. 3,725,072, No. 3.73
No. 0.722, No. 3,891,445, No. 3.900
．． No. 483, No. 3.929.484, No. 3.93
3.500, 3, 973.968, 3.99
No. 0.896, No. 4,012,259, No. 4,02
No. 2,620, No. 4.029.508, No. 4,057
, No. 432, No. 4.106.942, No. 4,133,
No. 958, No. 4.269.936, No. 4.286.
No. 053, No. 4.304.845, No. 4.314,
No. 023, No. 4.336.327, No. 4.356
．． No. 258, No. 4,386,155, No. 4,401,
This is described in No. 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+ represents a halogen atom or an alkoxy group. R2 represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent.

R3 is an 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 an aryl group, which may have a substituent. Represents an oxy group. z
l represents a group that can be released upon coupling with the oxidized product of the color developing herbal medicine.

Specific examples of yellow dye-forming couplers are shown below.

[Exemplary compounds]

(Y-1) (Y-2) (Y-3) (Y-4) t (Y-5) L (Y-6) (Y-7) (Y-8) (Y-9) (Y- 10) t- (Y-11) t (Y-12) L (Y-13) (Y-14) (Y-15) L (Y-16)

(Ct (Y-1'?) (Ct Y-4) Ct Y -+q) Ct (Y-20) Ct (Y-2i) Ct (Y-22) Ct (Y-23) t (Y-24) Ct (Y-2'; ) Ct 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] Ar L In the formula, Ar represents an aryl group, Ra1 represents a hydrogen atom or a substituent, and Ra2 represents a substituent. Y is a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent, and W is -NH-1-NHCO- (N atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCON.
represents H-, and ■ is an integer of 1 or 2; ) Specific example of the following five phrase Ca) - 4ct t In the magenta coupler represented by the above general formula [aI] General formula [aI], Za is a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle. represents the la
The ring formed by may have a substituent.

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, Ra represents a hydrogen atom or a substituent.

Examples of the substituent represented by Ra include a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, siam L subo compound residue, Organic hydrocarbon compound residues, alkoxy groups, aryloxy groups, heterocyclic oxy groups, siloxy groups, acyloxy groups, carbamoyloxy groups, amino groups,
Acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group Can be mentioned.

″-Prfa These include, for example, U.S. Patent No. 2,600,788, U.S. Pat.
Same No. 3.127.269, No. 3,311,476, No. 3,152,896, No. 3.419.391
No. 3,519,429, No. 3.555.31
No. 8, No. 3,684,514, No. 3,888,6
No. 80, No. 3,907,571, No. 3,928,
No. 044, No. 3,930, No. 861, No. 3,930
, 866, 3,933,500, etc., JP-A-49-29639, 1ii149-111631
No. 49-129538, No. 5G-13041,
No. 52-58922, No. 55-62454, No. 5
No. 5-118034, No. 5G-38043, No. 57-
35858, 6G-23855, British Patent No. 1,247,493, Belgian Patent No. 769,1
No. 16, No. 792,525, West German Patent No. 2,156,
Specifications of No. 111, Japanese Patent Publication No. 46-60479, Japanese Patent Publication No. 59-125,732, Japanese Patent Publication No. 59-228, 252, Japanese Patent Publication No. 59-162,548, Japanese Patent Publication No. 59-171,956
No. 60-33.552, No. 400-43,659, West German Patent No. 1,070,030 and US Patent? , No. 725,067.

Typical cyan dye-forming couplers are phenolic and naphthol-based 4-equivalent or 2-equivalent type cyan dye image-forming couplers, and are disclosed in U.S. Pat. No. 2,306,410.
No. 2,356,475, No. 2,362.59
No. 8, No. 2,367.531, No. 2,369,9
No. 29, No. 2,423.730@, No. 2,474,
No. 293, No. 2.476, No. 008, No. 2□498
．． No. 466, No. 2,545,687, No. 2,72
No. 8,660, No. 2,772,162, No. 2.8
No. 95.826, No. 2,976.146, No. 95.826, No. 2,976.146, No.
No. 3,002,836, No. 3,419,390, No. 3,446,622, No. 3,476.563,
Same No. 3.737゜316, Same No. 3.758.308@
, No. 3.839.044, British Patent No. 478,99
No. 1, No. 945.542, No. 1,084,480
No. 1,377.233, No. 1,388,02
No. 4 and winter version 11 of No. 1,543,040, and JP-A No. 47-37425, No. 50-10135, l.
m5O-25228, 5G-112 (No. 138,
No. 50-117422, fil 50-13044
No. 1, No. 51-6551, QSl-37647,
No. 51-528284, No. 51-108841, No. 5
No. 3-109630, No. 54-48237, No. 54-
No. 66129, No. 54-131931, No. 55-3
No. 2071, No. 59-146,050, No. 59-3
It is described in publications such as No. 1,953 and No. 6G-117,249.

As the cyan-forming coupler, the following general formula [E] [F]
Couplers represented by can be preferably used.

General Formula [E] In the formula, R1 represents an aryl group, a cycloalkyl group, or a heterocyclic group. R2 represents an alkyl group or a phenyl group. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

Zl represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary @amine color developing agent.

General formula [F] 2F In the formula, R4 is an alkyl group (e.g. methyl group, ethyl group,
propyl group, butyl group, nonyl group, etc.). R5 represents alkyl S<eg, methyl group, ethyl group, etc.).

R6 is a hydrogen atom, a halogen atom (e.g. fluorine, chlorine,
(bromine, etc.) or an alkyl group (eg, methyl group, ethyl group, etc.).

'Z2 represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the surface of silver halide crystals can be processed using solid dispersion methods, latex dispersion methods, oil-in-water emulsion dispersion methods, and various other methods. This method can be selected as appropriate depending on the chemical structure of the hydrophobic compound such as the coupler.The oil-in-water emulsion dispersion method is a method for dispersing hydrophobic additives such as the coupler. can be applied, and is usually dissolved in a high boiling point organic solvent with a boiling point of about 150°C or higher, if necessary in combination with a low boiling point and/or water-soluble organic solvent, and a surfactant is added to a hydrophilic binder such as an aqueous gelatin solution. Using a stirrer, homogenizer,
It may be emulsified and dispersed using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, and then added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point oils include phenol derivatives that do not react with the oxidized form of the developing agent, phthalates, phosphates, citric esters, benzoates, alkylamides,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150
An organic solvent having a temperature of ℃ or higher is used.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

Between the emulsion layers of the photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or reducing sharpness. Color anti-capri agents are used to prevent deterioration and graininess from becoming noticeable.

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

In the light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

Ultraviolet absorbers are added to the protective layer, intermediate layer, and other aqueous colloid layers of the photosensitive material of the present invention to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to U light. May contain.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photographic light-sensitive material using the silver halide emulsion of the present invention is used to reduce the gloss of the light-sensitive material, to increase the writeability, and to create a bond between the light-sensitive materials. A matting agent can be added to prevent scratching.

A tank of photographic material using the silver halide emulsion of the present invention! Lubricants can be added to reduce chafing.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Various surfactants are used for the purposes of preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitization).

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

The silver halide material of the present invention can be prepared directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, or
It may be applied via one or more subbing layers (to improve wear resistance, hardness, antihalation properties, friction 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 to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

An image can be formed using the silver halide photographic material of the present invention by subjecting it to a color development treatment known in the art.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds generally have a concentration of about 0.1 g to about 300% for color developer 11, preferably about 1 g to about 15% for color developer 11.
Used at a concentration of 111.

Examples of aminophenol-based developers include O-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and 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-〇-phenylenediamine hydrochloride, N,
N'-dithymer-p-7 enylenediamine hydrochloride, 2
-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-human O-oxyethylaminoaniline, 4
-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline, -p
-Toluenesulfate and the like can be mentioned.

In addition to the above-mentioned primary aromatic amine color developer, well-known developer component compounds can be added to the color developer applied to the processing of the silver halide photographic material of the present invention. For example, alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates,
Alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included.

The color developer typically has an EIH value of 7 or higher, most commonly from about 10 to about 13.

The silver halide photographic material according to the present invention may contain these color developing agents in the hydrophilic colloid layer either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath. The color developing agent brecasa is a compound that produces a color developing agent under alkaline conditions, and includes a Schiff 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. Precursors for these aromatic primary amine color developing agents are disclosed, for example, in U.S. Pat. Nos. 3,342,599 and 2,5.
No. 07.114, No. 2,695,234, No. 3.
719.492, British Patent No. 803.783, JP-A-53-185628, JP-A-54-790
35 issues of each publication, Research Disclosure Magazine 15
It is described in No. 159, No. 12146, and No. 13924.

These aromatic primary amine color developing agents or their precursors need to be added in such an amount that sufficient color development can be obtained upon activation treatment. The amount varies depending on the type of light-sensitive material, but is generally between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate it into a photosensitive material, it can be added by dissolving it in a suitable solvent such as water, methanol, ethanol, acetone, etc.
It can be added as an emulsified dispersion using a high-boiling organic solvent such as dioctyl phthalate or tricresyl phosphate, or it can be added by impregnating a latex polymer as described in Research Disclosure No. 14850.

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be performed simultaneously with fixing treatment. Many compounds are used as bleaching agents, among them iron (I), cobalt (■), and copper (II).
polyvalent metal compounds, especially complex salts of these polyvalent metal cations and organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-human Oxyethylethylenediaminediacetic acid, malonic acid,
Metal complex salts or ferricyanates such as tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, weight O
Mumate salts and the like may be used alone or in suitable combinations.

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 an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination. The stabilizing liquid used in the stabilization treatment may contain a pH adjuster, a chelating agent, an anti-piping agent, and the like. For these specific conditions, reference may be made to JP-A-58-134,636 and the like.

[Specific Effects of the Invention] According to the present invention, red-sensitive silver halide grains having a silver chloride content of 80 mol% or more are combined with a specific dye and a specific hardener, thereby achieving high sensitivity and low capri Thus, it is possible to obtain a silver halide photographic material that is suitable for rapid processing and satisfies recent demands for high productivity.

Furthermore, it is possible to obtain a silver halide photographic light-sensitive material that exhibits little desensitization or increase in fog over time and allows for high-yield printing.

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

Example 1 A total of 14 types of samples were prepared by coating the following 1st to 7th layers on a reflective support made of polyethylene-coated paper.

11th - Blue-sensitive silver chloride emulsion layer A silver chloride emulsion formed by sensitizing silver chloride grains with an average grain size of 0.8 μm to blue, yellow coupler (Y-29) and 2,5-di-t- An emulsified dispersion prepared by dissolving octylhydroquinone in dioctyl phthalate was used for coating.

2nd m--First intermediate layer 2.5-di-t-octylhydroquinone was dissolved in dioctyl phthalate and an emulsified dispersion was prepared.

Third layer... Green-sensitive silver chlorobromide emulsion layer A silver chloride emulsion formed by green-sensitizing silver chloride grains with an average grain size of 0.5 μm, magenta coupler (m-5) and 2.5-di An emulsified dispersion prepared by dissolving -t-octylhydroquinone in dioctyl phthalate was used for coating.

4th layer...Second intermediate layer: The following ultraviolet absorber (LJV-1) and 2.5-di-t
- An emulsified dispersion prepared by dissolving octylhydroquinone in dioctyl phthalate was used for coating.

5th layer...Red-sensitive silver chlorobromide or silver chloride emulsion layer table-2
Silver chlorobromide particles with an average particle size of 0.5μ■ containing silver chloride as shown in Table 1, or a sodium chloride aqueous solution and a silver nitrate aqueous solution were added to an inert gelatin aqueous solution at 50°C and the pA (+ was controlled to be 7.0). The average particle size was 0.5 μm, monodisperse S-0 was added by double jet method for 60 minutes.
, 14 cubic silver chloride grains as a red sensitizing dye (IV-7)
A red sensitized emulsion and a cyan coupler (C
-5) and an emulsified dispersion prepared by dissolving 2.5-di-t-octylhydroquinone in dioctyl phthalate, and a 3% aqueous solution of the dye shown in Table 2 were used for coating.

6th layer...Third intermediate layer The following ultraviolet absorber (UV-1) and 2,5-Z-T
- An emulsified dispersion prepared by dissolving octylhydroquinone in dioctyl phthalate was used for coating.

No. 711: Protective layer was coated mainly using gelatin and a hardening agent shown in Table 2.

JV-1 Amount of main components in each layer < man per 10oct')
are shown in Table-1.

Table-2 () is the name of each ingredient! <IQ/10Gcf).

*marked indicates sample of the present invention [maximum absorption wavelength of water-soluble dye in gelatin film] 1 [
-1674n11 m-7675rim ■-13(transition)l [)-1650nm D-2675nIIl [)-3730nm D-1 C)-1 H-/ C0CH==CH2 H-λ CH25αcH=H2 H2C=Hco□SH, C-C-C,L/, SO2,C
1-/2C/-/2cl-12S et al.C/-/lie CH.

H-1t Yomer 4 Alcohol,) I-2/Tips 7t Run 1
In addition, the performance of a total of 14 types of samples (sample numbers 1 to 14) prepared in this way (sample numbers 1 to 14) was evaluated using the method shown below, and the results are shown in Table 3. Summarized.

(1) After filling and exposing the sensitive samples, sample numbers 1 to 4 are subjected to standard treatment steps (A) and (B), and sample numbers 5 to 14 are subjected to standard treatment step (B). The red density of the image was measured using a Sakura color densitometer PDA-60.
Relative sensitivity was determined by setting the sensitivity of sample 2 as 100. In the standard processing step (B) for sample numbers 1 to 4, low sensitivity and soft images were obtained, making them unsuitable for rapid processing.
For the evaluation of 4, the standard treatment process (A) was used.

Standard processing step A> (processing temperature and processing time) [1] Color development 38°C 3 minutes 30 seconds [2] Bleach constant if
33℃ 1 minute 30 seconds [3] Washing treatment 25-30
℃ 3 minutes [4] Drying 75-80℃ Approximately 2 minutes Processing solution composition (color development tank solution) Benzyl alcohol 15 dEthylene glycol 15-Potassium sulfite
2. OQ potassium bromide
0.79 Sodium Chloride
0.2g potassium carbonate 3
G, OQ hydroxylamine sulfate [3, OQ polyphosphoric acid (TPPS) 2.503-
Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate
5゜5Q fluorescent whitening agent (4,4'-diaminostilbenzsulfone armpit derivative) 1.017
Potassium hydroxide 2. h Add water and bring the total amount to ij! Bind and adjust pH to 10,20.

(Bleach-fix tank solution) Ferric ammonium ethylenediaminetetraacetate dihydrate 60Q ethylenediaminetetraacetic acid 3g Ammonium thiota (70% solution) 10 (hN Ammonium sulfite (40% solution) 27.51fi potassium carbonate or glacial acetic acid p ) l Adjust to 7.1 and add water to bring the total volume to 1.
Set to 1.

Standard processing step B> (Processing temperature and processing @) [1] Color development 35°C 50 seconds [2] ~ [4] Same color development tank liquid composition as standard processing step <A> Ethylene glycol 1G Frog N, N '
-Diethylhuman O-xylamine 2-potassium chloride
2g N-ethyl-N-β-sulfonamidoethyl-3-methyl-4-amino-aniline sulfate 5g sodium tetrapolyphosphate 2g potassium carbonate
300 adenine
Add 0.002Q pure water to make 11, pi-1
Adjust to -10.08.

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

(3) Desensitization over time Sample stored for 3 months at 25°C and 60% relative humidity (A)
The respective relative sensitivities SA and SB of the fresh comparative sample (B) were determined by the method shown in (1) Sensitivity.

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

(5) Infrared sensor fogsharp infrared light emitting diode GL-350 (Gallium-
The sample was exposed to light for 5 minutes at a distance of 5 cm from an arsenic type (arsenic type) light source, and the exposed sample was subjected to standard treatment.
Cyan concentration was measured using a type densitometer.

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

Among the samples in which the silver chloride content of silver halide was 100 mol %, samples 10 and 11 using hardeners other than those of the present invention showed large fog and fog over time. In addition, in samples 12, 13 and 14 using dyes other than the present invention,
Desensitization over time is large, resulting in a significant decrease in yield.

On the other hand, in samples 5 to 9 according to the present invention,
It satisfies all performance requirements in terms of high productivity, high yield, and high image quality.

Example 2 The yellow coupler used in the first layer in Example 1 was (
Add the magenta coupler used for the third layer to (Y-35) (1-
3), and the silver amount was changed to 4 cm per 100 Ct', the cyan coupler used in the fifth layer was changed to (C-6), and the red sensitizing dye was changed for sample numbers 23 and 24, sample number 27.28 For this, 10-3 mol of the following anti-capri agent was added per 1 mol of silver halide to give a total of 1 as shown in Table 4.
Table 5 shows the results of creating four types of samples and evaluating all the obtained samples in the same manner as in Example 1 using the standard treatment process (8).
summarized in.

Table 4 *Anti-capri agent was added to sample number 27.28. The amount of each component added (sg7100c1g) is shown in parentheses.

, 71, 1, $1 agent [As is clear from the results in H05 Table 3, 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. However, the sample according to the present invention exhibited the effects of the present invention that could be confirmed in Example 1.

Further, even if the red sensitizing dye was changed, the effects of the present invention were similarly achieved.

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

Patent applicant Konishiroku Photo Industry Co., Ltd.
i, I process (method) % formula % 2. Name of the invention Silver halide photographic light-sensitive material 3. Relationship to the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Keio Ide 4, Agent 102 Address 1-1 Kudankita 4-chome, Chiyoda-ku, Tokyo (Delivery date) June 24, 1986 6, The power of attorney subject to amendment and the entire text in the details...(Contents changed) None) 7. Contents of amendment

Claims (5)

[Claims] (1) In a silver halide 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 on a support, at least the red-sensitive silver halide emulsion layer is provided. The emulsion layer has a silver chloride content of 8
contains silver halide grains that are 0 mol% or more, and
Hardened with a compound represented by the following general formula [I] and/or a compound represented by the following general formula [II],
Further, the silver halide photographic light-sensitive material is characterized in that it contains a water-soluble bispyrazolone pentamethine oxonol dye having a maximum absorption wavelength of 660 nm to 680 nm in the gelatin film. . General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 is a chlorine atom, a hydroxy group, an 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);
R_2 has the same meaning as R_1 excluding the chlorine atom. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_3 and R_4 are each a chlorine atom, hydroxy group, alkyl group, alkoxy group, or -OM group (M
represents a monovalent metal atom), -Q- and -Q
'- represents a linking group of -O-, -S- or -NH-, respectively, and L represents an alkylene group or an arylene group. l and m each represent 0 or 1. (2) The silver halide grains contained in the red-sensitive silver halide emulsion layer and having a silver chloride content of 80 mol% or more are monodisperse silver halide grains. Silver halide photographic material according to item 1. (3) The halogenated compound according to claim 1 or 2, wherein the red-sensitive silver halide emulsion layer contains silver halide grains having a silver chloride content of 90 mol% or more. Silver photosensitive material. (4) A patent claim characterized in that the water-soluble bispyrazolone pentamethine oxonol dye having a maximum spectral absorption in the wavelength range of 660 to 680 nm in a gelatin film is a compound represented by the following general formula [III]. A silver halide photographic material according to Item 1, Item 2, or Item 3 of the scope. General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_5 and R_6 are each -CN or -CO
OR_9 represents an alkyl group or an aryl group. L represents a methine group. R_7 and R_8
each represents an aliphatic group, an aromatic group or a heterocyclic group. (5) Silver halide grains having a silver chloride content of 80 mol % or more contained in the red-sensitive silver halide emulsion layer are selected from sensitizing dyes represented by the following general formula [IV] or [V]. 5. The silver halide photographic material according to claim 1, which is color sensitized with at least one sensitizing dye. General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1_0 and R_1_1 each represent an alkyl group or an aryl group, L_1, L_2, L_3
, L_4 and L_5 represent methine groups. Z_1 and Z_2 each represent an atom or atomic group necessary to complete the oxazole ring, thiazole ring or selenazole ring. Z_3 represents a group of hydrocarbon atoms necessary to form a 6-membered ring. X^■ represents an acid anion. m_1
, m_2, n and l_1 each represent 0 or 1. However, when the compound forms an inner salt, l is 0.