JP3467658B2 - Silver halide photographic light-sensitive material and its development processing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material containing a dye, and more specifically, a novel silver halide photographic light-sensitive material which is less affected by emulsions such as fog and desensitization and is bleached during rapid processing and has excellent residual color. The present invention relates to a silver halide photographic light-sensitive material containing a different diffusion resistant dye.

[0002]

2. Description of the Related Art Conventionally, silver halide photographic light-sensitive materials (hereinafter abbreviated as photographic light-sensitive materials) have a specific wavelength for the purpose of light absorption filter, antihalation, irradiation prevention or sensitivity adjustment of photosensitive emulsion. It is well known to incorporate a dye into a constituent layer of a photographic light-sensitive material in order to absorb the light, and dyeing a hydrophilic colloid layer with the dye has been performed. Dyes for the purpose of substituting yellow colloidal silver in color photographic light-sensitive materials, dyeing dyes for crossover cut layers in X-ray photographic light-sensitive materials, dyes for dyeing non-photosensitive emulsion layers in printed photographic light-sensitive materials It has spread.

The dye used for such a purpose has not only good absorption spectrum characteristics depending on the purpose of use but also is completely decolorized during development processing and easily eluted from the photographic light-sensitive material. , No residual color contamination by dye after processing, no adverse effect such as fog or desensitization on photosensitive emulsion, no diffusion from colored layer to other layers, in photographic light-sensitive material or coating solution In the above, it must satisfy various conditions such as excellent stability over time and no discoloration or fading.

To date, many studies have been carried out with the aim of finding dyes satisfying the above conditions.
For example, U.S. Patents 3,540,887, 3,544,325 and 3,560,
No. 214, Japanese Patent Publication No. 31-10578 and Japanese Patent Publication No. 51-3623 disclose benzylidene dyes, and British Patent No. 506,385 and Japanese Patent Publication No.
Oxonol dyes in US Pat. No. 2,493,747 in 9-22069
No. 1,845,404, and styryl dyes are proposed in US Pat. No. 1,845,404.

Some of these conventional dyes have a relatively small effect on the emulsion performance and have the ability to be bleached / eluted / bleached in the processing step, but from the viewpoint of diffusion resistance. It was not enough to see. That is, when a specific layer of a plurality of emulsion layers is selectively colored and used as a filter layer or an antihalation layer, not only the diffusion to other layers is remarkable, but the light absorption effect is lowered,
There was a defect that it gave an unfavorable effect to other layers such as sensitivity deterioration, gradation change and fog abnormality.

As a means for preventing the dye from diffusing into other layers, the dye itself is made diffusion resistant, for example, US Pat. No. 2,538,008.
No. 2,539,009, 4,420,555, JP-A-61-204630
Nos. 62-32460 and 63-184749 are disclosed. Each of these dyes has a drawback that the decolorizing property and the solubility in a processing liquid are inferior, resulting in residual color contamination. Also, a dissociative dye is fixed using a mordant,
As a method for making the material resistant to diffusion, for example, US Pat.
Nos. 3,625,694 and 4,124,386 are disclosed. However, the method using a mordant is a binder in the photographic light-sensitive material constituting layer, for example, gelatin, which forms an aggregate with the mordant or increases the viscosity, which causes serious problems such as uneven coating and cissing. In addition, there are drawbacks such as inconvenience, diffusion resistance between layers is not sufficient, elution and decoloring properties during treatment are poor, a treatment bath having a high pH is required, and rapid treatment suitability is poor.

Further, as a means for preventing the diffusion of the dye, there is a method of dyeing a specific layer with a solid fine particle dispersion of a dye which is water-insoluble and easily dissolved in a solution having a high pH, for example, US Pat. No. 4,855,221, No. 4,857,446, No. 4,948,717
No. 52-92716, No. 55-155350, No. 55-155351
No. 56-12639, No. 63-197943, JP-A-2-110453
No. 2, No. 2-1838, No. 2-1839, No. 2-119942, No. 2-2642
No. 47, No. 2-264936, No. 2-277044, No. 4-37841, and World Patent No. 88/04794 are disclosed. However, the method, although the effect as a means of diffusion resistance of the dye is seen, there is a drawback that a dye having a desired absorption spectrum is difficult to obtain, decolorization in rapid processing can not be said to be sufficient, There was still a problem of residual color contamination. Therefore, even in rapid processing, there is a strong demand for a diffusion resistant dye that has good decolorizing properties and does not cause residual color contamination after processing.

[0008]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which has the above-mentioned requirements for a diffusion-resistant dye, has little fog and has improved stability over time. is there.

Another object is to provide a silver halide photographic light-sensitive material having high sensitivity and excellent sharpness. Another object of the present invention is to provide a silver halide photographic light-sensitive material which gives an image with little residual color contamination by a short development process.

[0010]

The above objects of the present invention have been achieved by the following constitutions.

1) A silver halide photographic light-sensitive material having at least one non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye represented by the following general formula ( 3 ) on a support. Regarding the general formulas (1) and (2) that serve as references
Will be sequentially described below.

[0012]

[Chemical 6]

In the formula, D represents a nitrogen atom, N ⁺ R ₁ (R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group or an alkenyl group), O ⁺ or S ⁺ , and Z ₁ represents a hetero atom. Represents a group of non-metal atoms necessary for forming a ring, Q represents an aryl group or a heterocyclic group, X ⁻ represents an anion, k represents 0 or 1, m represents 0 or 1, and n Represents ₁ , 2 or 3, and L ₁ , L ₂ , L ₃ and L ₄ represent a substituted or unsubstituted methine group. However, at least one of L _{1 and} L ₂ is a methine group substituted with an electron-withdrawing group having a Hammett's substituent constant σp value of 0.3 or more.

2) A dye represented by the general formula ( 3 ) has a carboxyl group, a sulfamoyl group, a sulfonamide group, or
1) having at least one phenolic hydroxyl group
The described silver halide photographic light-sensitive material.

[0015]

It is preferable that the dye represented by the general formula (1) is a dye represented by the following general formula (2).

[0017]

[Chemical 7]

In the formula, R ₂ , R ₃ , R ₄ , and R ₅ represent a hydrogen atom or a substituent, and Z ₂ represents a nonmetallic atom group necessary for forming a 5-membered or 6-membered heterocycle. , Y represents NR ₈ (R ₈ represents a hydrogen atom, a substituted or unsubstituted alkyl group or an alkenyl group), an oxygen atom or a sulfur atom, Q represents an aryl group or a heterocyclic group, and X ⁻ represents an anion. Represents
k represents 0 or 1, m represents 0 or 1, n is 1, 2
Or 3, and L ₁ , L ₂ , L ₃ , and L ₄ represent a substituted or unsubstituted methine group. However, at least one of L ₁ or L ₂ is substituted with a group selected from a cyano group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, or a trifluoromethyl group. Represents a methine group, which is a carboxyl group, sulfamoyl group,
It has at least one of a sulfonamide group or a phenolic hydroxyl group.

[0019]

[0020]

[Chemical 8]

In the formula, R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom or a substituent, R ₆ and R ₇ represent a substituted or unsubstituted alkyl group or aryl group, and R ₆ and R ₇ And may combine with each other to form a ring, R ₈ represents a hydrogen atom, a substituted or unsubstituted alkyl group or alkenyl group, Q represents an aryl group or a heterocyclic group, and X ⁻ represents an anion. , K
Represents 0 or 1, n represents 1, 2 or 3, and L ₁ or L ₂ represents a substituted or unsubstituted methine group. However, at least one of L ₁ or L ₂ is substituted with a group selected from a cyano group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, or a trifluoromethyl group. And has at least one of a carboxyl group, a sulfamoyl group, a sulfonamide group or a phenolic hydroxyl group in the molecule.

3 ) The silver halide photographic feeling described in 1 ) above.
Optical material, emulsion layer or other hydrophilic colloid layer
Containing a small amount of the hydrazine derivative represented by the following general formula (4)
A silver halide photographic light-sensitive material containing at least one kind. 4) At least one kind of solid fine particle dispersion is a support and a halo.
Included in hydrophilic colloid layer between silver genide emulsion layers
The silver halide photographic light-sensitive material described in 3) above .

[0023]

[0024]

[0025]

[Chemical 10]

In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, B represents a hydrogen atom, an alkyl group, an aryl group,
Represents an alkoxy group, an aryloxy group or an amino group,
G is -CO- group, -COCO- group, -SO ₂ - represents a group, -SO- group, a thiocarbonyl group or an iminomethylene group.

5 ) A development processing method, which comprises processing the silver halide photographic light-sensitive material described in 1) above for a total processing time of 90 seconds or less.

6 ) A development processing method characterized in that the silver halide photographic light-sensitive material described in 1) above is processed for a total processing time of 45 seconds or less.

The present invention will be described in more detail below.

The dye represented by formula (1), (2) or (3) will be described.

Examples of the heterocyclic group containing Z ₂ in the general formula (2) include quinolyl group, isoquinolyl group, indolyl group, benzimidazolyl group, benzofuryl group, benzothienyl group, benzthiazolyl group, benzoxazolyl group, indolenyl group. , Benzimidazolyl group, benzthiopyrylium group and the like.

The aryl group represented by Q in the general formula (1), (2) or (3) is a phenyl group, a naphthyl group or a julolidyl group, and the heterocyclic group is a pyridyl group, a quinolyl group or an isoquinolyl group. Group, pyrrolyl group, indolyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, furyl group, benzofuryl group, thienyl group, benzothienyl group, thiazolyl group, benzothiazolyl group,
Examples thereof include an oxazolyl group and a benzoxazolyl group.

A heterocyclic group represented by Z ₁ in the general formula (1),
And a heterocyclic group containing Z ₂ of the general formula (2), an aryl group and a heterocyclic group represented by Q of the general formula (1), (2) or (3) include those having a substituent, Examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, a cyano group, a hydroxy group, a mercapto group, an amino group, an alkoxy group, Examples thereof include an aryloxy group, an acyl group, a carbamoyl group, an acylamino group, a ureido group, a sulfonamide group, and a sulfamoyl group, and these substituents may have two or more kinds in combination. As a preferable substituent, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group,
Ethyl group, t-butyl group, n-octyl group, 2-hydroxyethyl group, 2-methoxyethyl group, etc.), hydroxy group, cyano group, halogen atom (eg fluorine atom, chlorine atom, etc.), carbon number 1-6 An alkoxy group (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, methylenedioxy group, n-butoxy group, etc.), substituted amino group (eg, dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group, etc.), carboxy group, carbamoyl group (eg carbamoyl group, methylcarbamoyl group, ethyl Carbamoyl group, butylcarbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group Group, etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group etc.), acyl group (eg methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group,
Phenylcarbonyl group, 4-ethylsulfonamide phenylcarbonyl group, etc., sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (eg, sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group) Etc.),
You may combine these substituents.

In the substituted or unsubstituted methine group represented by L ₁ and L ₂ of the general formula (1), (2) or (3), and L ₃ and L ₄ of the general formula (1) (2) In the substituted or unsubstituted methine group represented, as the substituent, a heterocyclic group represented by Z ₁ of the general formula (1), and a heterocyclic group containing Z ₂ of the general formula (2), Examples of the substituent on the aryl group and the heterocyclic group represented by Q in the general formula (1), (2) or (3) include the groups shown above.

L _{1 of the} general formula (1), (2) or (3)
And at least one of the substituted or unsubstituted methine groups represented by L ₂ is an electron-withdrawing group, and the electron-withdrawing group is represented by the substituent constant Hammett's σp value (edited by Toshio Fujita). , "Chemical Region Special Issue No. 122, Structure-Activity Relationship of Drugs", 96-103 (1979) Nankodo, etc.) is preferably 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, methoxycarbonyl). Base,
Ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc., aryloxycarbonyl group (eg phenoxycarbonyl group, 4-hydroxyphenoxycarbonyl group), carbamoyl group (eg carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, butylcarbamoyl group) Group, dimethylcarbamoyl group,
Phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, etc.), acyl group (for example, methylcarbonyl group,
Ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group, 4-ethylsulfonamidophenylcarbonyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, etc.), arylsulfonyl group ( For example, phenylsulfonyl group, 4-chlorosulfonyl group, etc.),
Examples thereof include trifluoromethyl group.

D in the general formula (1) is a nitrogen atom, N ⁺ R ₁ (R ₁
Represents a hydrogen atom, a substituted or unsubstituted alkyl group or an alkenyl group. ), O ⁺ or S ⁺ , and Y in the general formula (2) is NR ₈ (R ₈ represents a hydrogen atom, a substituted or unsubstituted alkyl group or an alkenyl group), an oxygen atom or a sulfur atom. The alkyl group represented by R ₁ and the alkyl group represented by R ₈ in the general formulas (2) and (3) are preferably an alkyl group having 1 to 8 carbon atoms, for example, Methyl group, ethyl group, n-propyl group, isopropyl group, n-octyl group, 2-methoxyethyl group, N,
N-dimethylcarbamoylmethyl group, 3-carboxypropyl group, 4-sulfobutyl group, 3-hydroxypropyl group, 4-
Examples thereof include a carboxybutyl group, and the alkenyl group is preferably an alkenyl group having 1 to 6 carbon atoms, such as an allyl group, a 2-butenyl group, a 3-butenyl group and a 3-carboxy-1-
Examples thereof include a propenyl group.

R ₂ , R ₃ , R _{4 of} the general formulas (2) and (3),
R ₅ represents a hydrogen atom or a substituent, and as the substituent, a heterocyclic group represented by Z ₁ in the general formula (1), and a heterocyclic group containing Z ₂ in the general formula (2), General formula (1),
Examples of the substituents on the aryl group and the heterocyclic group represented by Q in (2) and (3) include the groups shown above.

In the general formula (3), R ₆ and R ₇ represent a substituted or unsubstituted alkyl group or alkenyl group, and R ₆ and R ₇ may combine with each other to form a ring. Examples of the alkenyl group include groups represented by R _{1 of} the general formula ( ₁ ) and R ₈ of the general formulas (2) and (3). The ring formed by combining R ₆ and R ₇ with each other includes a substituted or unsubstituted cyclohexyl ring, a benzene ring, a carbon condensed ring (for example, a naphthalene ring, a tetralin ring, etc.), a hetero condensed ring (for example, a quinoline ring, Tetrahydroquinoline ring, julolidine ring, etc.) and the like.

X ^{− of the} general formula (1), (2) or (3)
In Examples of the anion represented, halogen ions (Cl ^-, B
^{r -, I -), ClO} 4 -, p- toluenesulfonate ion, ethyl sulfate ion, and the like.

In the dye represented by the general formula (1) of the present invention, the dye represented by the general formula (2) is preferable, and the dye represented by the general formula (3) is more preferable.
Further, it is particularly preferable to use the general formula (1), (2) or (3)
In the above, it is a dye having at least one of a carboxyl group, a sulfamoyl group, a sulfonamide group or a phenolic hydroxyl group in the molecule.

Specific examples of the dye of the present invention are shown below, but the scope of the present invention is not limited to these.

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

[0045]

[Chemical 14]

[0046]

[Chemical 15]

[0047]

[Chemical 16]

[0048]

[Chemical 17]

[0049]

[Chemical 18]

[0050]

[Chemical 19]

The following is a specific synthesis example of the dye used in the present invention.

Synthetic Example 1 Illustrative dye 11 4-N, N-dimethylaminocinnamaldehyde (1.56 g) and 2-cyanomethyl-6-hydroxycarbonyl-1-methyl-3,3-dimethylindolium iodide (3.00 g) were mixed with acetic anhydride. The mixture was mixed in 10.0 ml and reacted under heating under reflux for 3 hours. The precipitate was filtered off and thoroughly washed with ethanol. The crude crystals were suspended in 50 ml of methanol, washed by suspension, separated by filtration, and dried to obtain 3.1 g of blue-violet crystals. The structure of the obtained dye is NM
It was confirmed by R spectrum and mass spectrum.

A method for producing a solid fine particle dispersion of a dye according to the present invention is described in JP-A-52-92716 and JP-A-55-15535.
No. 0, 55-155351, 63-197943, 3-182743,
The method described in WO88 / 04794 or the like can be used. Specifically, it can be prepared by using a surfactant and using a fine disperser such as a ball mill, a vibration mill, a planetary mill, a sand mill, a roller mill, a jet mill or a disc impeller mill. Further, after dissolving the dye in a weak alkaline aqueous solution, a method of precipitating fine particulate solids by lowering the pH to weakly acidic or a weak alkaline solution of the dye and an acidic aqueous solution are simultaneously mixed while adjusting the pH. Dispersions of dyes can be obtained by the method of making finely divided solids. The dyes may be used alone or in combination of two or more. Two
When two or more species are mixed and used, they may be dispersed individually and then mixed, or may be simultaneously dispersed.

The dye dispersed in the form of solid fine particles according to the present invention is preferably dispersed so that the average particle diameter is 0.01 μm to 5 μm, more preferably 0.01 μm to 1 μm, and particularly preferably 0.01 μm. ~ 0.5 μm. Also,
The coefficient of variation of particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. Here, the variation coefficient of the particle size distribution is a value represented by the following formula.

(Standard deviation of particle size) / (Average value of particle size) × 100 A surfactant may be used in the production of the solid fine particle dispersion of the dye, and the surfactant may be an anion. Any of the cationic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, but, for example, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates are preferred. , Anionic surfactants such as sulfosuccinates, sulfoalkyl polyoxyethiene alkylphenyl ethers, N-acyl-N-alkyl taurines and nonionic interfaces such as saponins, alkylene oxide derivatives, alkyl esters of sugars It is an activator.

The surfactant may be added at any position before dispersion, during dispersion or after dispersion, but it is preferably added before the dispersion of the dye is started. Further, if necessary, it may be added to the dye dispersion liquid after the dispersion is completed. These anionic activators and / or nonionic activators may be used alone or in combination of two or more, and both activators may be used in combination. The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the conditions of the dispersion liquid of the dye, etc.
It may be 0.1 to 2000 mg per 1 g of dye, preferably 0.5 to 100
It may be 0 mg, more preferably 1 to 500 mg. The concentration of the dye in the dispersion liquid is 0.01 to 10% by weight, preferably 0.1 to 5% by weight.

To the dye dispersion of the present invention, a hydrophilic colloid used as a binder for a photographic constituent layer can be added before the start of dispersion or after the end of dispersion. As the hydrophilic colloid, it is advantageous to use gelatin, but in addition, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin and phthalated gelatin, and gelatin and a monomer having a polymerizable ethylene group can be used. Graft polymers, carboxymethyl cellulose, hydroxymethyl cellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-
Synthetic hydrophilic polymers such as N, N-dimethylacrylamide, poly-N-vinylpyrrolidone and polymethacrylic acid, agar, gum arabic, alginic acid, albumin and casein can be used. You may use these in combination of 2 or more types.

The dispersion of the dye of the present invention is used for a layer constituting a photographic light-sensitive material, for example, a non-photosensitive hydrophilic colloid layer such as an emulsion layer upper layer, an emulsion layer lower layer, a protective layer, a support undercoat layer and a backing layer. be able to. The preferred amount of dye used is
Depending on the type of dye and the characteristics of the photographic light-sensitive material, it is not uniform, but the optical density in the photographic light-sensitive material may vary from 0.05 to 0.05 depending on the purpose.
Used to achieve 3.0, 1 mg per 1 m ^{2 of} photographic light-sensitive material
To 1000 mg, more preferably 3 mg to 500 mg, particularly preferably 5 mg to 250 mg.

In the photographic light-sensitive material of the present invention, the solid fine particle dispersion of the dye may be contained in at least one non-photosensitive hydrophilic colloid layer. Gelatin is preferred as the hydrophilic colloid, and its coating amount is preferably
0.01 g / m was ^{2 ~2.0g} / m ^2, more preferably 0.1 g /
m ² was ~1.7g / m ^2, particularly preferably 0.2 g / m ² to 1.4
g / m ² .

The photographic light-sensitive material of the present invention may have at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer on one side of the support, and A photographic light-sensitive material having the emulsion layer and the colloid layer on both sides of the support is also preferably used. Photographic materials include medical X-ray photographic materials, printing plate photographic materials, color negative photographic materials, color reversal photographic materials, color photographic paper photographic materials, direct positive photographic materials, and heat-developable color photographic materials. , Diffusion transfer type color photographic materials and the like.

The gelatin used in the photographic light-sensitive material of the present invention is generally produced from cow bone, cow hide, pig skin, etc. as a raw material. In the process of producing collagen, gelatin treated with lime etc., alkali treated gelatin, hydrochloric acid, etc. There is acid-processed gelatin accompanied by the treatment with, and any gelatin can be used in the present invention. For details of the manufacturing method and properties of these gelatins, see, for example, “T by Arthur Veis”.
he Macromolecular Chemistry of Gelatin '', 187-217
P. (1964) (Academic Press), TH James, The Theor
y of the photographic Process '' 4th.ed, p. 55 (1977)
(Macmillan), "Nawakawa and Gelatin", published by Japan Nawa Gelatin Industry Association (1987), "Basics of Photographic Engineering-Silver Salt Photographs", pp. 119-124 (Corona). The jelly strength of gelatin (by PAGI method) is preferably 250 g
That is all. The calcium content of the gelatin of the present invention (PAGI
Method) is preferably 4000 ppm or less, particularly preferably 3000 ppm or less.

Gelatin is hardened by a hardener, and the swelling ratio and film strength of the coating film can be adjusted by the amount of hardener in the photographic light-sensitive material. Examples of hardening agents include aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), mucohalogenoic acids (mucochloric acid, mucophenoxycycloric acid, etc.), epoxy compounds, active halogen compounds (2,4-dichloro-6-hydroxy-s). -Triazine etc.), active vinyl derivatives (1,3,5-triacryloylhexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis (β- (vinylsulfonyl
(Propionamide) etc.) ethyleneimines, carbodiimides, methanesulfonic acid esters, organic hardeners such as isoxazoles, inorganic hardeners such as chromium alum, U.S. Patents 3,057,723, 3,396,029, 4,161,407 Polymer hardeners and the like described in No. etc. can be used,
Used alone or in combination. In the photographic light-sensitive material of the present invention, the swelling ratio of the coating film during development processing is preferably 150 to 250%, and the film thickness after expansion is preferably 70 μm or less. The swelling rate means the difference between the film thickness after swelling in each processing solution and the film thickness before the development processing, and this is divided by the film thickness before processing and multiplied by 100, and the swelling rate is 250. If it exceeds%, poor drying occurs, and if the swelling ratio is less than 150%, uneven development and residual color tend to deteriorate during development.

The halogenated emulsion used in the photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
Although any of silver chloroiodobromide, silver chloride and the like can be used, silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide are particularly preferable.

The silver halide grains in the photographic emulsion are all isotropically grown crystal type such as cube, octahedron, and tetrahedron, or polyhedral crystal type such as sphere, and plane defects. It may be of a twin crystal having, or a mixed type or a composite type thereof. The grain size of these silver halide grains may be from fine grains of 0.1 μm or less to large grains of 15 μm.

The emulsion used in the photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), pages 22-23
1; Emulsion Preparation and Types and No. 18716 (November, 1979), p.648. Also, TH James, "The theory of the
photographic process "4th edition, published by Macmillan (1977) 3
The method described on pages 8 to 104, "Photographic Emulsion Chemistry", Focal Press by GF Daufin
Published by P.Glafkides, "Physics and Chemistry of Photography", published by 1966, Ch
imie et Physique Photographique ", published by Paul Montel (1
967), VL Zelikman et al., "Manufacturing and Coating of Photographic Emulsions".
Making and Coating Photographic Emulsion ", Focal Pr
It is prepared by the method described in ess company (1964) and the like.
In other words, particle preparation such as forward mixing method, back mixing method, double jet method, controlled double jet method, etc., conversion method, core / shell method, etc. under solution conditions such as neutral method, acidic method, ammonia method, etc. It can be manufactured using conditions and combinations of these.

The silver halide emulsions preferably used in the present invention are, for example, JP-A-59-177535 and 61-802238.
No. 61-132943, No. 63-49751, and the like, high internal iodine type monodisperse particles are disclosed. The crystal habit may be a cube, an octahedron, a tetrahedron, or an intermediate (111) plane and (100) plane. The monodisperse emulsion referred to here is a halogen having at least 95% of the grains by number or weight within ± 40% of the average grain size, preferably within ± 30% when the average grain diameter is measured by a conventional method. It is a silver halide grain. The grain size distribution of the silver halide grains may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The definition of monodispersity described here is described in JP-A-60-162244, and the coefficient of variation with respect to particle diameter is 0.2 or less.
The crystal structure of silver halide may be composed of different silver halide compositions inside and outside. For example, a core / shell type monodisperse emulsion having a two-layer structure composed of a high-iodity core portion and a low-iodity shell layer can be mentioned. A method for producing a monodisperse emulsion is known, for example, JP-A-48-36890 and JP-A-52-16364.
Nos. 55-142329, 58-49938, 60-14331, British Patents 1,027,146, 1,413,748, U.S. Patents 3,505,06.
No. 8, No. 3,574,628, No. 3,655,394, No. 4,444,877 and the like.

The silver halide emulsion preferably used in the present invention includes tabular grains having an aspect ratio of 3 or more. The advantages of such tabular grains include improved spectral sensitization efficiency and improved image graininess and sharpness. For example, British Patent 2,112,157 and U.S. Pat.
Issue 4,433,048, Issue 4,414,310, Issue 4,434,226,
JP-A-58-113927, 58-127921, 63-138342,
No. 63-284272, No. 63-305343, etc.,
The emulsion can be produced by the methods described in these publications. The tabular silver halide grains according to the present invention are preferably monodisperse emulsions having a narrow grain size distribution, and the coefficient of variation is preferably 25% or less, more preferably 20% or less, particularly preferably 15%. % Or less. As tabular silver halide grains, at least 80% or more of the total projected area of silver halide grains contained in the emulsion should have an aspect ratio of 3.0 to 12.0 indicated by the (grain size) / (thickness) ratio. Is preferred, and more preferably the aspect ratio is 3.
0 to 8.0. The thickness of tabular silver halide grains is 0.05.
~ 1 μm is preferable, more preferably 0.05 ~
0.5 μm. If the average of the ratio (t / l) of the longest distance (l) between two or more parallel twin planes of the tabular silver halide grain and the thickness (t) of the tabular grain is 5 or more, It is preferably, and more preferably 7 or more. The tabular silver halide grain preferably used is a core / shell type grain, for example, a double structure type grain having a silver halide composition in which the inside of the grain is different from the surface thereof, JP-A-61-24515.
Examples thereof include multi-structured particles shown in No. 1 and the like.

As a silver halide solvent, for example, ammonia, a thioether compound, a thione compound or the like can be used in order to control the growth of grains during the formation of silver halide grains. Also, during physical aging and chemical aging, zinc,
A metal salt such as lead, thallium, iridium or rhodium can coexist. The silver halide can be sensitized with a noble metal salt such as a sulfur compound or a gold salt. Further, reduction sensitization can be performed, and these methods can be combined for sensitization. Further, a silver halide spectrally sensitized to a desired wavelength region with a spectral sensitizing dye can be used. Dyes used include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl dye, and hemioxonol dye, and particularly useful dyes belong to cyanine, merocyanine, and complex merocyanine dyes. It is a pigment.

It is possible to The photographic light-sensitive material of the present invention can be obtained by coating an emulsion prepared by dispersing the above silver halide in a hydrophilic colloid medium, for example, in gelatin on a polyethylene terephthalate or triacetate cellulose support. For the cross-linking of gelatin, aldehydes such as glyoxal and mucochloric acid, cyanuric acid, aziridine, vinyl sulfones and the like can be used.

When the photographic light-sensitive material of the present invention is applied for printing plate making, a high-contrast image is formed in the light-sensitive silver halide emulsion layer or a hydrophilic colloid layer adjacent to the light-sensitive silver halide emulsion layer for adjusting the gradation. A hydrazine compound or a tetrazolium compound may be contained as an agent, an amine compound may be contained as a contrast enhancing agent, or a redox compound which releases a development inhibitor by a redox reaction during development may be contained.

As the hydrazine compound, --NH in the molecule
A compound having an NH- group, which is preferably a compound represented by the following general formula (4).

[0072]

[Chemical 20]

In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, B represents a hydrogen atom, an alkyl group, an aryl group,
Represents an alkoxy group, an aryloxy group or an amino group, and G represents a —CO— group, a —COCO— group, a —SO ₂ — group, a —SO—
Represents a group, a thiocarbonyl group or an iminomethylene group.

The general formula (4) will be described in more detail. The aliphatic group represented by A is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and may be branched or cyclic. A
The aromatic group represented by is preferably a monocyclic or condensed ring aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocyclic group represented by A is preferably a monocyclic or condensed ring heterocyclic group containing at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and examples thereof include a pyridyl group, a quinolyl group and an imidazolyl group. ,
Examples thereof include furyl group, thienyl group, thiazolyl group, benzothiazolyl group, pyrrolidyl group and morpholyl group. These aliphatic group, aromatic group or heterocyclic group may have a substituent, and examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an alkylthio group, an amino group, a ureido group, a sulfamoyl group and a carbamoyl group. Group, a sulfonamide group, an acylamino group, a hydroxy group, a halogen atom, a cyano group, an acyl group, an alkoxycarbonyl group, a carboxy group and the like, preferably, an alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms Alkoxy group, carbon number 1
An amino group substituted with 20 alkyl groups, a sulfonamide group having 1 to 30 carbon atoms, and an acylamino group having 1 to 30 carbon atoms. A is preferably an aryl group or an aromatic heterocyclic group. Particularly preferably, A is an aryl group or an aromatic heterocyclic group having a diffusion resistant group or a silver halide adsorption promoting group. As the anti-diffusion group, a ballast group used as an immobilizing group for a photographic coupler (eg, an alkyl group and its derivative having 10 or more carbon atoms in total, an aryl group and its derivative) is preferable, and a halogenated group is preferable. As the silver adsorption promoting group, a thiourea group, a thiourethane group, a mercapto group, a thioether group,
Thione group, mercapto heterocyclic group, thioamide heterocyclic group,
Examples thereof include a sulfur-containing heterocyclic group or an adsorption group described in JP-A-64-90439.

As G in the general formula (4), particularly --CO--
The group, -COCO- group is preferable.

The alkyl group represented by B in the general formula (4) is an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, octyl group, methoxyethyl group, 2-hydroxyethyl group, 3-methane). (Sulfonamidopropyl group, etc.) are preferred, and the aryl group is a monocyclic or bicyclic aryl group (eg, phenyl group, 3-methanesulfonamidophenyl group, 4-cyanophenyl group, 4-acetylphenyl group, naphthyl group, etc.) The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms (eg, ethoxy group, butoxy group, 2-methoxyethoxy group, etc.), and the aryloxy group is a monocyclic or bicyclic aryloxy group (eg, phenoxy group). Group, 4-methanesulfonylphenyl group, 4-
Cyanophenyl group, naphthyloxy group, etc.) are preferable,
As the amino group, a mono-substituted or di-substituted amino group (eg, methylamino group, dimethylamino group, propylamino group, anilino group, dimethoxyethylamino group, N-
Ethyl-N-methanesulfonylethylamino group, 2,2,6,6-
Tetramethylpiperidylamino group, morpholino group, pyrrolidyl group and the like) are preferable.

Preferred hydrazine compounds include JP-A-3-36540, JP-A-6-194774 and US Pat. No. 4,269,9.
No. 29, for example 1-formyl-2-{[4- (n-butylureido) phenyl]} hydrazine, 1-formyl-2- {4- [2- (2,4 -Di-tert-pentylphenoxy) butyramide] phenyl} hydrazine, 1- (2,2,
6,6-Tetramethyl-4-piperidylaminooxalyl) -2-
{4- [2- (2,4-Di-tert-pentylphenoxy) butylamido] phenyl} hydrazine, 1- {4- (2,2,6,6-tetramethylpiperidyl) aminooxalyl} -2- {4- 〔2- (2,4-di-te
rt-Pentylphenoxy) butyramide] phenylsulfonamidephenyl} hydrazine, 1- {4- (2,2,6,6-tetramethylpiperidyl) aminooxalyl} -2- {3- [1-phenyl-1′-p- Chlorophenylmethylthioacetamidophenyl] sulfonamidophenyl} hydrazine, 1-formyl-2-{[4- (2- (2- (2-ethoxy) ethoxy) ethoxy) ethylthioacetamidophenyl] sulfonamidophenyl} hydrazine, 1- ( N-pyridinium methylcarbonyl)-
2-{[4- (2- (2- (2-ethoxy) ethoxy) ethoxy) ethylthioacetamidophenyl] sulfonamidophenyl}
Examples include hydrazine.

The hydrazine compound is added by adding alcohols such as methanol and ethanol, ethylene glycols,
It can be added after being dissolved in ethers, ketones and the like, and the addition amount is 10 ^-6 to 10 ^-1 mol, preferably 10 ^-4 to 10 ^-2 mol per mol of silver halide. A photographic light-sensitive material containing a hydrazine compound can be subjected to a development treatment with a developer having a pH of 10.8 or less for a development time of 30 seconds or less to give a contrast of 10 or more.

Examples of the tetrazolium compound include compounds described in JP-A No. 3-15039, for example, 2,3-di (p-methoxyphenyl) -5-phenyltetrazolium chloride; 2,3-di ( Examples include p-methylphenyl) -5-phenyltetrazolium chloride and 2,3,5-tri (p-methylphenyl) tetrazolium chloride.

Examples of the tetrazolium compound include compounds described in JP-A No. 3-15039. For example, 2,3-di (p-methoxyphenyl) -5-phenyltetrazolium chloride; 2,3-di ( Examples include p-methylphenyl) -5-phenyltetrazolium chloride and 2,3,5-tri (p-methylphenyl) tetrazolium chloride.

The amine compound as a contrast-increasing aid contains at least one nitrogen atom and is disclosed in, for example, JP-A-57-120434.
No. 57, No. 57-129435, No. 57-129436, No. 60-129746,
56-94347, 60-140340, 60-218642, 60-6
6248, U.S. Pat.Nos. 417,498, 3,021,215, and
3,046,134, 3,523,787, 3,746,545, and
No. 4,013,471, No. 4,038,075, No. 4,072,523, No. 4,0
The compounds described in 72,526 and the like can be appropriately selected and used.

The redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones and the like as redox groups, and 5-nitroindazole and 4-nitroindazole as development inhibitors. , 1-phenyltetrazole, 1- (3-sulfophenyl) tetrazole, 5-
It is a compound having nitrobenztriazole, 4-nitrobenzotriazole, 5-nitroimidazole, 4-nitroimidazole and the like, and examples thereof include compounds described in JP-A No. 3-249643 and US Pat. No. 4,269,929. The redox compound is added by methanol, ethanol, ethylene glycol, triethylene glycol, propylene glycol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate,
It can be added after being dissolved in an organic solvent such as acetone or methyl ethyl ketone. Further, those which are difficult to dissolve in water or an organic solvent can be added after being dispersed in the form of solid fine particles by high speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like. The addition amount is from 10 ^-6 to 10 ^-1 mol, and preferably from 10 ^-4 , per mol of silver halide.
It is 10 ^-2 mol. Preferred redox compounds include:
For example, 2- (stearylamide) -5- (1-phenyltetrazole-5-thio) hydroquinone, 2- (2,4-di-t-amylphenopropionamide-5- (5-nitrotriazol-2-yl) )
Hydroquinone, 2-dodecylthio-5- (2-mercaptothiothiadiazole-5-thio) hydroquinone, 1- (4-nitroindazol-2-yl-carbonyl) -2-{[4- (n-butylureido) phenyl] Hydrazine, 1- (5-nitroindazol-2-yl-carbonyl) -2- {4- [2- (2,4-di-tert-pentylphenoxy) butyramide] phenyl} hydrazine,
1- (4-nitrotriazol-2-yl-carbonyl) -2- {4-
[2- (2,4-di-tert-pentylphenoxy) butyramide]
Phenyl} hydrazine, 1- (4-nitroimidazol-2-yl-carbonyl) -2- {4- [2- (2,4-di-tert-pentylphenoxy) butyramide] phenylsulfonamide phenyl} hydrazine, etc. be able to.

Various techniques and additives known in the art can be used in the silver halide photographic light-sensitive material of the present invention, if necessary. For example, in addition to the photosensitive silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer,
Photographic layers such as a crossover light cut layer and a backing layer can be provided, and in these layers, a supersensitizer, a coupler, a high boiling point solvent, an antifoggant, a stabilizer, a development inhibitor, and a bleaching agent can be provided. Accelerator, fixing accelerator, anti-color mixing agent, formalin scavenger, toning agent, hardener, surfactant,
A thickener, a plasticizer, a slip agent, an ultraviolet absorber, a polymer latex, an antistatic agent, a matting agent and the like can be contained by various methods. As the support which can be used in the silver halide photographic light-sensitive material of the present invention, cellulose triacetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, polyethylene and the like are laminated. Paper, glass, metal, etc. can also be used. The surface of these supports is provided with an undercoat layer to improve the adhesion of the coating layer, or is subjected to an undercoating process such as corona discharge or ultraviolet irradiation as required.

The above-mentioned additives are described in more detail in Research Disclosure No. 17643 (December 1978).
No. 18716 (November 1979), No. 308119 (December 1989)
Month). The types of compounds shown in these Research Disclosures and their locations are shown below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 648 Upper right 996 Sensitizing dye 23 648-649 996-8 Desensitizing dye 23 998 B Dye 25-26 649-650 1003 Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 649 Upper right 1006-7 Whitening agent 24 998 Hardener 26 651 Left 1004-5 Surfactant 26-27 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006 to 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008 to 9 XVI Binder 26 XXII 1009 XXII Support 28 XVII 1009 XVII Silver halide photographic light-sensitive material of the present invention Can be processed by, for example, The Theory of
The Photographic Process 4th Edition (TheTheory
of the Photographic Process, fourth Edition) 293-1
Page 34 and the Journal of the American Chemical S
ociety) Volume 73, page 3,100 (1951). Specific examples of the developing agent include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-).
Pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone), aminophenols (eg p-aminophenol, N-methyl-p-aminophenol), 1-phenyl-3-pyrazolins, ascorbic acid, etc. They can be used alone or in combination. The photographic light-sensitive material according to the present invention can be developed by rapid processing in which the development processing time from development to drying is 90 seconds or less, and can also be processed by rapid processing in which the development processing time is 45 seconds or less. You can Furthermore, development processing can be performed even by rapid processing with a development processing time of 30 seconds or less. The treatment temperature is preferably 25 to 50 ° C, more preferably 30 to 40 ° C.

[0086]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of seed emulsion-1) Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy disuccinate Na salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 824 g iodine Potassium bromide 23.5 g Water to make 2825 ml D1 1.75N Potassium bromide aqueous solution Solution A1 solution B1 and solution A1 using the mixing stirrer described in JP-B-58-58288 and 58-58289 at the following silver potential control amount of 35 ° C. Solution C1 46 each
Nucleation was carried out by adding 4.3 ml by the simultaneous mixing method over 1.5 minutes.

After stopping the addition of solution B1 and solution C1, it took 60 minutes to raise the temperature of solution A1 to 60 ° C., adjust the pH to 5.0 with 3% potassium hydroxide, and then re-solution. 55.4 ml / each of B1 and solution C1 by the simultaneous mixing method
It was added for 42 minutes at a flow rate of min. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during this temperature increase from 35 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B1 and C1 was +8 mv each using the solution D1. And +
Controlled to be 16mv. After the addition was completed, the pH was adjusted to 6 with 3% potassium hydroxide, and the mixture was immediately desalted and washed with water.

In this seed emulsion, 90% or more of the total projected area of silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains had an average thickness of 0.06 μm and an average grain size ( It was confirmed by an electron microscope that the circle diameter was 0.59 μm. The variation coefficient of thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Emulsion Em-1) A seed emulsion-1 and the following solution were used to prepare a tabular emulsion Em-1 having a core / shell structure.

A2 ossein gelatin 11.7 g polypropylene oxy-polyethylene oxy-disuccinate Na salt (10% ethanol aqueous solution) 1.4 ml seed emulsion-1 equivalent to 0.10 mol B2 ossein gelatin 5.9 g potassium bromide 6.2 g potassium bromide Potassium iodide 0.8g Finished with water to 145ml C2 Silver nitrate 10.1g Finished with water to 145ml D2 Ocein gelatin 6.1g Potassium bromide 94g Finished with water 304ml E2 Silver nitrate 137g Finished with water 304ml A2 liquid vigorously stirred at 67 ℃ The solution B2 and the solution C2 were added by the double jet method in 58 minutes. Next, in the same liquid, D2
Solution and E2 solution were added by the double jet method in 48 minutes. During this time, pH was kept at 5.8 and pH was kept at 8.7 throughout.

After completion of the addition, desalting and precipitation were carried out in the same manner as in seed emulsion-1, and the average silver iodide contents of pAg 8.5 and pH 5.85 at 40 ° C were obtained.
An emulsion of 0.5 mol% was obtained.

Observation of the obtained emulsion with an electron microscope revealed that tabular silver halide grains having an average grain size of 0.96 μm in 81% of the projected area and a broad grain size distribution of 19% and an average aspect ratio of 4.5. Met. The average distance between twin planes is 0.019 μm.
And the coefficient of variation was 28%.

Next, after the emulsion (Em-1) was heated to 60 ° C.,
After adding the specified amount of spectral sensitizing dye as a solid fine particle dispersion, dissolve adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate mixed aqueous solution and triphenylphosphine selenide in a mixed solvent of ethyl acetate and methanol. The resulting solution was added, and after 60 minutes, a silver iodide fine grain emulsion was added, and ripening was performed for a total of 2 hours.
4-hydroxy-6-methyl-1,3, as a stabilizer at the end of aging
A predetermined amount of 3a, 7-tetrazaindene (TAI) was added.

The above-mentioned additives and their addition amounts (per mol of AgX) are shown below.

Spectral sensitizing dye (SD-1) 2.0 mg Spectral sensitizing dye (SD-2) 120 mg Adenine 15 mg Ammonium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg Silver iodide Fine particle emulsion 280 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 50 mg A solid fine particle dispersion of a spectral sensitizing dye is disclosed in Japanese Patent Application No. 4-99437.
It was prepared according to the method described in No. That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature had been adjusted to 27 ° C. in advance, and the mixture was stirred by a high speed stirrer (dissolver) at 3,500 rpm for 30 to 120 minutes to obtain the dye.

The average iodine content of the outermost surface of the silver halide grains contained in the silver halide emulsion (Em-1) was about 4 mol% by the addition of the above silver iodide fine grain emulsion. The following additives were added to the emulsion thus sensitized to prepare an emulsion layer coating solution, and at the same time, a protective layer coating solution was prepared.

Next, a blue-colored polyethylene terephthalate film base for X-rays having a density of 0.15 (thickness: 175 μm
The copolymer aqueous dispersion obtained by diluting both sides of m) so that the concentration of the copolymer consisting of three kinds of monomers of glycidyl methacrylate 50 wt%, methyl acrylate 10 wt% and butyl methacrylate 40 wt% is 10 wt% is obtained. After coating and undercoating, the following dye layers were coated on both sides of the support. Further, the emulsion layer coating solution and the protective layer coating solution were simultaneously multi-layer coated in the following predetermined coating amounts and dried.

First layer (dye layer) Solid fine particle dispersion dye Amount shown in Table 1 Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4-dichloro-6 -Hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² The solid fine particle dispersion of the dye is based on the method described in World Patent 88/04794. It was made. That is, in a 60 ml screw cap container, 21.7 ml of water and the surfactant Triton X.
-200 (manufactured by Rohm & Haas) and 6.7% solution 2.65g, and put into this solution 1.0g powdered dye in a mortar,
40 ml of zirconium oxide beads (2 mm diameter) were added. After the cap was closed and placed in a ball mill and dispersed at room temperature for 4 days, 8.0 g of a 12.5% gelatin aqueous solution was added and mixed well, and the zirconium oxide beads were filtered and removed to obtain a solid fine particle dispersion of the dye.

Second Layer (Emulsion Layer) The following various additives were added to the emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butylcatechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000 ) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenylphosphonium chloride 20 mg / m ² 1, Ammonium 3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound (M) 5 mg / m ² compound (N) 5 mg / m
² colloidal silica (average particle size 0.014μm) 0.5g
/ M ² latex (L) 0.2 g / m ² dextrin (average molecular weight 1000) 0.2 g / m ² However, gelatin was adjusted to 1.0 g / m ² .

Third Layer (Protective Layer) Gelatin 0.8 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7 mg / m ² Polymethyl methacrylate matting agent 50 mg / m ² (Area average particle size 7.0 μm) Formaldehyde 20 mg / m ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² Bis (vinylsulfonylmethyl) ether 36 mg / m ² latex (L ) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound (S-2) 5 mg / m ² C ₉ F ₁₉ —O— (CH ₂ CH ₂ O ) _11- H 3mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) (CH ₂ CH ₂ O) _15- H 2mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) _{(CH 2 CH 2 O) 4} - (CH 2) 4 SO 3 Na 1mg / m 2 of using It shows things below.

[0104]

[Chemical 21]

[0105]

[Chemical formula 22]

[0106]

[Chemical formula 23]

[0107]

[Chemical formula 24]

The amount of additive added was for one side, and the coated silver amount was adjusted to be 1.6 g / m ² for one side.

Each of the samples Nos. 1 to 10 thus obtained was stored under two kinds of storage conditions (condition A: 23 ° C./55% R
H, condition B: 40 ° C./80% RH), and the photographic performance was evaluated after storage for 4 days.

[Evaluation of Photographic Performance] Sample Two samples were obtained.
It is sandwiched between sheets of intensifying screen KO-250 (made by Konica Corporation), a tube voltage of 80 kvp, a tube current of 100 mA, and an X of 0.05 seconds through an aluminum wedge.
Exposure was performed by irradiating a line. Then automatic processor SR for rapid processing
X-502 (manufactured by Konica Corp.) was used for processing with a developer and a fixer having the following formulations.

The processed sample was subjected to density measurement with an optical densitometer PDA-65 (manufactured by Konica Corp.) to evaluate sensitivity, fog and residual color. Sensitivity is the reciprocal of the exposure amount at fog density + 0.5, and the sensitivity of sample No. 1 in Table 1 immediately after coating and drying is
It was shown by the relative value. The residual color was visually evaluated by treating the obtained sample without exposing it. The best sample with no residual color was set to 5, 1 was a level where the residual color was extremely bad, and 4 or more was a practical level. The evaluation of MTF was performed as follows. That is, an MTF chart containing a rectangular wave of 0.5 to 10 lines / mm of lead is displayed on a fluorescent screen KO-250 (Konica
(Made by Co., Ltd.) is closely adhered to the front side of the film, X-rays are irradiated so that the density of the part not shielded by the lead chart on the film surface becomes about 1.0 on both sides, and after development processing, recording The formed rectangular wave pattern was measured with a Sakura Microdensitometer M-5 type (manufactured by Konica Corp.). The aperture size at this time is 300 μm in the direction of the rectangular wave,
It was 25 μm in the perpendicular direction and the magnification was 20 times. M
The TF is shown as a value at a spatial frequency of 2.0 lines / mm. The results obtained are shown in Table 1.

<Preparation of processing agent> (Developer formulation) Part-A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% aqueous solution) 2280 g Sodium hydrogencarbonate 132 g Diethylenetetraamine 5 acetic acid 120 g 5-Methylbenzo Triazole 1.2g 1-Phenyl-5-mercaptotetrazole 0.2g Hydroquinone 340g Add water to finish to 5000ml Part-B (for 12 liter finish) Glacial acetic acid 170g Triethylene glycol 185g 1-Phenyl-3-pyrazolidone 22g 5-Nitroindazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water to make 1000 ml To about 5 l of water, add Part-A and Part-B above at the same time, make 12 l with water while stirring, and adjust pH to 10.4 with glacial acetic acid. Adjusted to. This is used as a development replenisher. 1 liter of this developer replenisher
On the other hand, 20 ml of the above-mentioned starter was added and the pH was adjusted to 10.26 to prepare a developing solution.

(Fixing solution formulation) Prat-A (for 18 l finishing) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethylamino) ) -Ethyl-5-mercaptotetrazole 18g Prat-B (for 18l finishing) Aluminum sulfate (anhydrous salt equivalent) 800g Part-A and Part-B are added at the same time to about 5l of water, and water is added with stirring to make 18l. Finish and adjust pH to 4.40 with sulfuric acid and sodium hydroxide.

The processing was carried out at development 35 ° C., fixing 33 ° C., water washing 20 ° C. and drying 50 ° C., respectively, and the processing time was dry to dry for 45 seconds.

[0115]

[Table 1]

As is clear from the results shown in Table 1, the photographic light-sensitive material containing the solid fine particle dispersion of the dye of the present invention has less adverse effects on photographic characteristics such as sensitivity and fog, and has excellent sharpness. Very little residual color contamination after processing,
It can be seen that it has excellent storage stability over time.

Example 2 In the same manner as in Example 1, Samples 18 to 31 were prepared by changing the coating amount of the solid fine particle dispersion of the dye according to the present invention. The coating amount of the dye is shown in Table 2. These samples are 23 ℃ / 55% RH
After storing for 4 days under the conditions described above, the sensitivity, fog and residual color were evaluated in the same manner as in Example 1. However, the treatment was carried out by using the developing solution and the fixing solution described in Example 1 at a developing temperature of 35 ° C., a fixing temperature of 33 ° C., a water washing temperature of 20 ° C. and a drying temperature of 50 ° C., and the processing time was dry to dry for 25 seconds. . The obtained results are shown in Table 2.

[0118]

[Table 2]

As is clear from the results shown in Table 2, the photographic light-sensitive material containing the solid fine particle dispersion of the dye of the present invention rarely adversely affects the photographic characteristics such as sensitivity and fog even in ultra-rapid processing, It can be seen that the residual color contamination after the treatment is extremely small.

Example 3 (Preparation of silver halide emulsion) 70 mol% silver chloride, 30 silver bromide
A silver nitrate aqueous solution and a mixed aqueous solution of NaCl and KBr were mixed by a controlled double jet method to grow silver halide grains so as to have a mol% silver halide composition. At this time, mixing was carried out under the conditions of 36 ° C., pH 7.8 and pH 3.0, and 2 × 10 ⁻⁷ mol of NaRhCl ₆ was added per 1 mol of silver during grain formation. After mixing, add the following SD-3 to 80 mg per mol of silver
added. After that, desalting was carried out with modified gelatin treated with phenylisocyanate to obtain the following compounds (A) and (B)
A bactericide consisting of the mixture of (C) and ossein gelatin were added and redispersed. The obtained emulsion was cubic grains having an average grain size of 0.2 μm and a coefficient of variation of 10%. The emulsion thus obtained contains 4-hydroxy-6- per mole of silver.
Add 60 mg of methyl-1,3,3a, 7-tetrazaindene, add 5 mg of chloroauric acid and 0.5 mg of sulfur flower per mol of silver, and add pH.
Chemical aging was carried out at 60 ° C for 80 minutes under the conditions of 5.8 and pAg7.5.
After completion of ripening, 900 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per 1 mol of silver, and further KI300 mg,
SD-4 350 mg was added.

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate films having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) An antihalation layer of the following formulation (1) was coated on the undercoat layer so that the amount of gelatin was 0.5 g / m ^2, and a silver halide emulsion layer of (2) had a gelatin amount of 2.6.
g / m ^2, by coating as the silver amount is 3.2 g / m ^2, further amounts gelatin 1.0 g / m protective layer having the following formulation (3) thereon
^It was painted so that it would be ² . On the other undercoat layer on the opposite side, a backing layer was coated according to the following prescription (4) so that the amount of gelatin would be 3.1 g / m ² , and on top of that, a protective layer of the following prescription (5). Was coated so that the amount of gelatin would be 1.0 g / m ² to prepare a sample.

Formulation (1) [Antihalation layer composition] Gelatin 0.5 g / m ² Solid fine particle dispersion dye Amount shown in Table 3 Surfactant: Sodium dodecylbenzenesulfonate 5 mg / m ² Colloidal silica (average particle size 0.014 μm 18 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Hardener: HD 25 mg / m ² A solid fine particle dispersion of dye was prepared in the same manner as in Example 1.

Formulation (2) [Silver halide emulsion layer composition] Gelatin 2.6 g / m ² Silver halide emulsion Silver amount 3.2 g / m ² Antifoggant: 4-mercaptobenzoic acid 2 mg / m ² 5-Nitroindazole 10 mg / M ² Nucleating agent: Z-1 3 × 10 ^-5 mol / m ² Nucleating accelerator: Z-2 1 × 10 ^-4 mol / m ² Polymer latex-1 1.0 g / m ² Colloidal silica (average particle size) Diameter 0.014 μm) 0.5 g / m ² Compound P 45 mg / m ² Water-soluble polymer: V-1 20 mg / m ² Surfactant: Saponin 0.1 g / m ² Sodium sulfosuccinate isopentyl normal decyl ester 8 mg / m ² Dura Agent: 2-hydroxy-4,6-dichloro-1,3,5-triazine 60 mg / m ² formulation (3) [emulsion protective layer composition] Gelatin 1.0 g / m ² Matting agent: 20 mg silica with an average particle size of 3.5 μm / M ² polymer latex 2 0.5 g / m
² Surfactant: sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg /
m ² Surfactant F-1 2 mg / m ² Accelerator: Hydroquinone 50 mg / m ² 1-Phenyl-4-hydroxymethyl-4′-methyl-3-pyrazolidone 5 mg / m ² Hardener: HD 30 mg / m ² Formulation (4) [Backing layer composition] Dye (D-1) 50 mg / m ² Dye (D-2) 40 mg / m ² Dye (D-3) 30 mg / m ² Gelatin 3.1 g / m ² Surfactant: Dodecyl Sodium benzenesulfonate 50mg / m ² 1-Phenyl-5-mercaptotetrazole 5mg / m ² Colloidal silica 0.4g / m ² Hardener: HD 60mg / m ² Formulation (5) [Backing protective layer composition] Gelatin 1g / m ² Matting agent: polymethylmethacrylate having an average particle size of 4.0 μm 50 mg / m ² Surfactant: sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² Hardener: HD 25 mg / m ² 2-hydroxy-4, Each compound using 6-dichloro-1,3,5-triazine 25 mg / m ² is shown below.

[0124]

[Chemical 25]

[0125]

[Chemical formula 26]

[0126]

[Chemical 27]

The obtained samples were evaluated by the following methods.

[Sensitivity and gamma] The obtained sample was brought into close contact with a step wedge, exposed to a tungsten light of 3200 ° K for 3 seconds, and subjected to development and fixing treatment to determine the sensitivity. The sensitivity is the reciprocal of the exposure amount that gives a fog density + 3.0 transmission density, and was determined as a relative value under each condition with the sensitivity of Sample No. 1 being 100. Further, gamma was obtained from the slope of the characteristic curve at the transmission density of 1.0 to 3.0. Gamma is practically
You need 10 or more.

[Dot quality] Dot area on the step wedge
A part of a 50% reticulated screen (150 lines / inch) is attached, the sample is brought into close contact with it, exposed for 5 seconds with a xenon light source, and the following development processing is performed to obtain a sample halftone quality of 100.
It was visually observed with a double magnifying glass, the sample having the best halftone dot quality was 5, 1 was an extremely bad level, and 4 or more was a practical level.

[Residual Color] The obtained sample was processed without being exposed to light, and five sheets were piled up and visually evaluated. The best sample with little residual color was set to 5, 1 was a level where the residual color was extremely bad, and 4 or more was a practical level.

The results obtained are shown in Table 3.

Processing was carried out under the following conditions with a rapid automatic developing machine using a developing solution and a fixing solution having the compositions shown below.

Developer formulation (composition A) Pure water (ion exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1- Phenyl-5-mercaptotetrazole 30 mg Potassium bromide 4.5 g Potassium hydroxide Amount to make the pH of the used solution 10.4 (Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When the developer was used, the above composition A and composition B were dissolved in 500 ml of water in this order, and the solution was made up to 1 liter.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Sodium citrate dihydrate 2 g Boric acid 6 g Acetic acid (90% aqueous solution) 13.6 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 26.5 g Water 500 ml when using fixer The above composition A and composition B were dissolved in this order, and the solution was finished to 1 liter and used. The pH of this fixer is about
It was 4.3.

Development processing conditions (Process) (Temperature) (Time) Development 35 ℃ 30 seconds Fixing 33 ℃ 20 seconds Rinse at room temperature for 15 seconds Dry 45 ℃ 15 seconds

[0136]

[Table 3]

As is clear from the results shown in Table 3, the photographic light-sensitive material containing the solid fine particle dispersion of the dye of the present invention has less adverse effect on photographic characteristics such as sensitivity and fog, and is excellent in halftone dot quality. It can be seen that the residual color contamination after development processing is extremely small.

Example 4 (Preparation of silver halide emulsion A) A silver chlorobromide emulsion consisting of 70 mol% of silver chloride and silver bromide as the balance was prepared by the simultaneous mixing method. At the time of simultaneous mixing, K ₃ RhBr ₆ was added at 8.1 × 10 ⁻⁸ mol per mol of silver. The obtained emulsion was a cubic emulsion having an average grain size of 0.20 μm and monodisperse grains (variation coefficient: 9%). The emulsion was then desalted with a modified gelatin described in JP-A-2-280139 (a gelatin having an amino group substituted with phenylcarbamyl, for example, G-8 in JP-A-2-280139).
The EAg after desalting was 190 mV at 50 ° C.

The emulsion thus obtained was adjusted to pH 5.58 and EAg123 mV, and the temperature was adjusted to 60 ° C. to give 1 mol of silver chloroauric acid.
× 10 ^-5 mol added and stirred for 2 minutes, then S8 per mol silver
2.9 × 10 ^-6 mol was added, and chemical ripening was further performed for 78 minutes.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7.5 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole 3.5 × 10 ^-4 mol and gelatin 28.4 g An emulsion liquid was added.

(Preparation of silver halide photographic light-sensitive material) An antihalation layer having the following formulation 1 was coated on one undercoat layer of 100 μm-thick polyethylene terephthalate film which had been subjected to the antistatic treatment described in Example 3. . On this upper layer, a silver halide emulsion having the following Formulation 2 is used, in which the silver amount is 3.3 g / m.
^{2. The} amount of gelatin was 1.7 g / m ² .

Furthermore, the following formulation 3 was provided as a protective layer on top of it.
Was coated so that the amount of gelatin would be 0.8 g / m ² . A backing layer of the following formulation 4 was coated on the opposite undercoat layer so that the amount of gelatin was 1.5 g / m ^2, and a protective layer of the following formulation 5 was coated on the upper layer with gelatin.
It was applied so as to be 1 g / m ² and the samples shown in Table 4 were prepared.

Formulation 1 (antihalation layer composition) Gelatin 0.4 g / m ² Solid fine particle dispersion dye Amount shown in Table 4 Alkanol-XC (manufactured by DuPont) 3.5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / M ² N, N'-methylenebis (β- (vinylsulfonyl) propionamide) 25 mg / m ²

[0144]

[Chemical 28]

Formulation 2 (composition of silver halide emulsion layers)

[0146]

[Chemical 29]

[0147]

[Chemical 30]

[0148] sulfosuccinate iso- amyl -n- decyl ester 0.64 mg / m ² 2-mercapto-6-hydroxy purine ^{1.7g / m 2 EDTA 50mg / m} 2 hydroquinone 50 mg / m ² Formulation 3 (Emulsion protective layer composition) Sodium sulfosuccinate iso-amyl-n-decyl ester 12mg / m ² Matting agent: Monodisperse silica 22mg / m ² 1,3-vinylsulfonyl-2-propanol 40mg / m ^{2 with} average particle size 3.5μm

[0149]

[Chemical 31]

Each coating solution on the emulsion side was adjusted to pH 5.5 with sodium acetate.

[0151] Formulation 4 (Backing layer composition) saponin 133 mg / m ² sulfosuccinate sodium iso- amyl -n- decyl ester 6 mg / m ² Colloidal silica (average particle size 0.014 .mu.m) 100 mg / ^{m 2}

[0152]

[Chemical 32]

Formulation 5 (composition of backing protective layer) Matting agent: monodisperse polymethylmethacrylate having an average particle diameter of 5.0 μm 50 mg / m
² Sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ^{2 The} obtained sample was brought into close contact with a step wedge and exposed at a wavelength of 633 nm as a substitute characteristic of He-Ne laser light, and then
A developer and a fixer having the following compositions were used and processed under the following conditions in an automatic processor for rapid processing (GR-26SR, manufactured by Konica Corporation).

(Developer Solution Formulation) Sodium sulfite 55 g / liter Potassium carbonate 40 g / liter Hydroquinone 24 g / liter 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (Dimeson S) 0.9 g / liter Potassium bromide 5 g / Liter 5-methyl-benzotriazole 0.13 g / liter boric acid 2.2 g / liter diethylene glycol 40 g / liter 6-propyl-2-thiouracil 60 mg / liter Add water and potassium hydroxide to make 1 liter / pH 10.4.

(Fixing liquid formulation) (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate ・ trihydrate 6.5 g Boric acid 6.0 g Sodium citrate ・ dihydrate 2.0 g (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ converted content is 8.1% W / V aqueous solution) 26.5 g The composition A and the composition B were melted in this order and finished to 1 liter before use. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development 35 ℃ 25 seconds Fixing 33 ℃ 17 seconds Rinse at room temperature for 15 seconds Dry 40 ℃ 30 seconds The results obtained are shown in Table 4 below.

[0157]

[Table 4]

As is clear from the results shown in Table 4, the photographic light-sensitive material containing the solid fine particle dispersion of the dye of the present invention hardly adversely affects photographic characteristics such as sensitivity and fog, and has excellent halftone dot quality. It can be seen that the residual color contamination after the development processing is extremely small.

When each of the above-mentioned samples of the present invention was similarly processed under the following development processing conditions, the sensitivity, fog and residual color were excellent.

[0160] (Process) (Temperature) (Time) Development 35 ℃ 15 seconds Fixing 33 ℃ 10 seconds Rinse at room temperature for 8 seconds Dry 50 ℃ 10 seconds

[0161]

The photographic light-sensitive material containing the solid fine particle dispersion of the dye of the present invention hardly adversely affects photographic characteristics such as sensitivity and fog, and has very little residual color contamination after development processing.

Front Page Continuation (72) Inventor, Yamato Komamura, Konica Co., Ltd. 1 Sakura-cho, Hino City, Tokyo (56) References JP-A-4-14033 (JP, A) JP-A-4-14038 (JP, A) ) JP-A-3-127052 (JP, A) JP-A-6-337506 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/83 G03C 1/06 501

Claims (6)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising at least one non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye represented by the following general formula ( 3 ) on a support. material. [Chemical 3] (In the formula, R ₂ , R ₃ , R ₄ , and R ₅ represent a hydrogen atom or a substituent.
R ₆ and R ₇ are a substituted or unsubstituted alkyl group or an ari.
Represents a group and R ₆ and R ₇ are bonded to each other to form a ring.
R ₈ may be a hydrogen atom, a substituted or unsubstituted
Represents a alkyl group or an alkenyl group, and Q represents an aryl group or
Represents a heterocyclic group, X ⁻ represents an anion, and k represents 0 or 1.
, N is 1, 2 or 3, L ₁ or L ₂ is a substituent or
Represents an unsubstituted methine group. However, each n L ₁
Alternatively, at least one of L ₂ is a cyano group or an acyl group.
Group, alkoxycarbonyl group, aryloxycarboni
Group, alkylsulfonyl group, arylsulfonyl group,
Selected from a carbamoyl group or a trifluoromethyl group
Represents a methine group substituted with a group
Voxyl group, sulfamoyl group, sulfonamide group or
Has at least one phenolic hydroxyl group. ) 2. The silver halide photograph according to claim 1, wherein the dye of the general formula ( 3 ) has at least one of a carboxyl group, a sulfamoyl group, a sulfonamide group or a phenolic hydroxyl group in the molecule. Photosensitive material. 3. A silver halide photographic light-sensitive material according to claim 1.
A material in an emulsion layer or other hydrophilic colloid layer
In addition, a small amount of hydrazine derivative represented by the following general formula (4)
A silver halide photographic light-sensitive material containing at least one kind . [Chemical 5] (In the formula, A represents an aliphatic group, an aromatic group, or a heterocyclic group.
Where B is a hydrogen atom, an alkyl group, an aryl group or an alkoxy group.
Represents a Si group, an aryloxy group or an amino group, and G represents -CO
- based on, -COCO- group, -SO ₂ - group, -SO- group, Chiokarubo
It represents a nyl group or an iminomethylene group. ) 4. At least one kind of solid fine particle dispersion is supported.
Hydrophilic colloid between carrier and silver halide emulsion layer
The silver halide photographic light-sensitive material according to claim 3 , wherein the silver halide photographic light-sensitive material is contained in a layer . 5. A silver halide photographic light-sensitive material according to claim 1.
Characterized by processing the charge with a total processing time of 90 seconds or less
Development processing method. 6. A silver halide photographic light-sensitive material according to claim 1.
Characterized by processing the charge in a total processing time of 45 seconds or less
Development processing method.