JPH0444033A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To dye a specific hydrophilic colloidal layer and to allow rapid decoloration during development processing by having the hydrophilic colloidal layer contg. solid fine particle dispersion of a specific dye. CONSTITUTION:This photosensitive material has the hydrophilic colloidal layer contg. the solid fine particle dispersion of the dye expressed by formula I. In the formula I, Q11 denotes 1, 3-indandione ring, isooxazolone ring, etc.; R11 denotes a hydrogen atom, alkyl group, etc.; R12 and R13 denote hydrogen atom, respectively or R12 and R13 denote the nonmetal atom group necessary for forming a 5- or 6-membered ring together with R14 and R15 respectively. R14, R15 respectively denote an alkyl group or aryl group or R14 and R16 may together form a 5- or 6-membered ring. L11, L12, L13 denote a methine group; n11 denotes 0, 1 or 2. The dyes of the dye layers have adequate spectral absorption and selectively dye the dye layers without diffusing to the other layers. The easy decoloration or elution is executed by photographic processing.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material in which a dye is used in a solid fine particle dispersion to prevent the dye from moving between hydrophilic colloid layers.

(Prior Art) In silver halide photographic materials, photographic emulsion layers and other hydrophilic colloid layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light incident on the photographic emulsion layer, a colored layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are multiple photographic emulsion layers, a filter layer may be located between them.

An image based on the fact that light scattered during or after passing through a photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the light-sensitive material on the opposite side of the emulsion layer and enters the photographic emulsion layer again. For the purpose of preventing blurring or halation, a colored layer called an antihalation layer is provided between the photographic emulsion layer and the support, or on the surface of the support opposite to the photographic emulsion layer. When there are multiple photographic emulsion layers, an antihalation layer may be placed between the layers.

Deterioration of image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation)
In order to prevent this, the photographic emulsion layer is also colored.

These hydrophilic colloid layers to be colored usually contain a dye. This dye needs to satisfy the following conditions.

(1) Must have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. That is, it should not have an adverse effect on the performance of the silver halide photographic emulsion layer in a chemical sense, such as a decrease in sensitivity, latent image regression, or fog.

(3) It should not be bleached during the photographic processing process or be eluted into the processing solution or washing water, leaving no harmful coloring on the photographic material after processing.

(4) Do not diffuse from the dyed layer to other layers.

(5) It has excellent stability over time in solutions or photographic materials and does not change color or fade.

In particular, when the colored layer is a filter layer or an antihalation layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are colored. In many cases, it is necessary to ensure that the

This is because otherwise it not only has harmful spectral effects on other layers, but also its effectiveness as a filter layer or antihalation layer is reduced. However, when a dyed layer and another hydrophilic colloid layer come into wet contact, it often occurs that some of the dye diffuses from the former to the latter. Many efforts have been made in the past to prevent such dye diffusion.

For example, a method in which a hydrophilic polymer with an opposite charge to a dissociated anionic dye is made to coexist in a layer as a mordant and the dye is localized in a characteristic layer by interaction with dye molecules is disclosed in US Pat. No. 2,548. No. 564, 4,124,3
No. 86, No. 3,625,694, etc.

In addition, a method of dyeing a specific layer using a water-insoluble dye solid is described in JP-A-56-], No. 2639, No. 55-1.
55350, 55-15535], 63-27
No. 838, No. 63-1.97943, European Patent No. 15
, No. 601, No. 274,723, No. 276.566, No. 299,435, No. 351.593, U.S. Patent No. 4,803,150, International Application Publication (WO) 8810
No. 4794 and the like.

In addition, a method of dyeing a specific layer using metal salt fine particles to which a dye has been adsorbed is disclosed in US Patent No. 2. 719. No. 088, No. 2,496.84+, No. 2,496.843, and Japanese Patent Application Laid-Open No. 60-45237.

However, even with these improved methods, the speed of decolorization during development processing is still slow, and if there are changes in various factors such as speeding up the processing, improving the processing solution composition, or improving the photographic emulsion composition. However, there was a problem in that the decolorizing function could not always be fully demonstrated.

In addition, when the silver halide photographic light-sensitive material is panchromatically sensitized, the antihalation dye is 400%
It is desirable to absorb light of nm to 700 nm. As such dyes, an example of using a monomethine oxonol dye and a pentamethine oxonol dye in combination is disclosed in JP-A-52-
92716, an example of using an arylidene dye and a pentamethine oxonol dye in combination is disclosed in JP-A-63-197943.
listed in the number. However, such a combination has the problem of decreased sensitivity and fog due to diffusion from the hydrophilic colloid layer containing the dye to other hydrophilic colloid layers.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a solid fine particle dispersion designed to dye a specific hydrophilic colloid layer in a photographic light-sensitive material and rapidly decolorize it during development. An object of the present invention is to provide a photographic material containing a dye.

(Means for Solving the Problems) The above object is achieved by a silver halide photographic light-sensitive material characterized by having a hydrophilic colloid layer containing a solid fine particle dispersion of a dye represented by the following general formula (I). achieved.

[In the formula, Q l l is 1. 3-indanedione ring, isoxacilone ring, 2,4-oxazolidinedione ring,
Represents a group of nonmetallic atoms necessary to form a barbituric acid ring or a thiobarbital acid ring.

Rlt represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, a halogen atom, or a cyano group. Rl 2, R+3 are each a hydrogen atom, R+2 is combined with R+4, or R13 is R
Represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring together with 15, respectively.

Rlt and R+5 each represent an alkyl group or an aryl group, or Rl (and Rl may be joined together to form a 5- or 6-membered ring. L II, L 12 and L 13 represent a methine group, n11 represents 0.1 or 2. Furthermore, the present invention contains a fixed fine particle dispersion of a dye represented by the general formula (I) above and a solid fine particle dispersion of a dye represented by the following general formula (n). A silver halide photographic material is provided.

(n) Q2□-ri, +L2゜-1-13+ 1121 Q 2
□, where R2+ and R25 are each a hydrogen atom,
Represents an alkyl group or an aryl group, R2□, R21,
R2 and R2g each represent an alkyl group, an aryl group, or 0R3
o, COOR3,, NR3, R3,, CONR3, R,
,,NR,,COR3,,COR3□,NR,,C0N
R3, R3,.

SO2Rs. or represents a cyano group, R21%R2□
represents a hydrogen atom, an alkyl group, an aryl group, COR32 or 5O2R32, provided that R30% R3+ each represents a hydrogen atom, an alkyl group or an aryl group, and R32
represents an alkyl group or an aryl group. ), L21. L
22 and L 23 each represent a methine group, n2 is 0,
Or represents 2. ] At least one nonmetallic atom group necessary to form a 1,3-indanedione ring, an isoxacilone ring, a 2,4-oxazolidinedione ring, a barbylic acid ring, or a thiobarbylic acid ring represented by Q l + It is preferable to have a carboxyl group or a sulfonamide group. More preferably, Q is 4 or 5-carboxy-1,
3-indanedione ring, 3-(2 or 3 or 4-carboxydiphenyl) isoxacilone ring, 3-(2 or 3 or 4-carboxyphenyl)-2,4-oxazolidinedione ring, 1-(2 or 3 or 4-Carphokydiphenyl)-3-alkyl or arylbarbylic acid ring or 1
-(2 or 3 or 4-carboxyphenyl)-3-alkyl or aryl-2thiobarbituric acid ring.

General formula (I) will be explained in detail.

The alkyl group represented by R11, R11 or RIK is
An alkyl group having 1 to 6 carbon atoms is preferable, and a substituent (for example, fluorine, chlorine, hydroxyl group, carboxyl group, cyan group,
ester group, substituted amino group, phenyl group, alkoxy group). Specifically, methyl, ethyl,
n-propyl, isopropyl, n-butyl, n-hexyl, hydroxyethyl, carboxymethyl, carboxyethyl, ethoxycarbonylmethyl, isopropyloxycarbonylethyl, cyanoethyl, methanesulfonamidoethyl, trifluoromethyl, benzyl, 4-carboxybenzyl, Examples include groups such as 2-methoxyethyl, 2-phenylsulfamoylethyl, 2-(2carboxybenzoyloxy)ethyl, and 2-dimethylaminoethyl.

The aryl group represented by Rl, Rlt or R+5 is preferably an aryl group having 6 to 10 carbon atoms, and a substituent (for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a carboxyl group, a sulfonamido group, an arylsulfonate group) (a moyl group, an ester group, a halogen atom, a cyano group, a hydroxyl group). Specifically, phenyl, naphthyl,
4-carboxyphenyl, 3-carboxyphenyl, 3
, 5-dicarboxyphenyl, 4-methoxycarbonylphenyl, 4-hydroxyphenyl, 2-hydroxyphenyl, 3-methoxy-4-hydroxyphenyl, 4-
Examples include groups such as methanesulfonamidophenyl, 4 q benzenesulfonamidophenyl, 2,4-dicarboxyphenyl, 4-cyanophenyl, 4-ethoxycarbonylphenyl, and 2-methyl-4-carphokydiphenyl.

The alkoxy group represented by Rl + has 1 to IO carbon atoms.
is preferably an alkoxy group, and a substituent (e.g., fluorine,
chlorine, hydroxyl group, carboxyl group, cyano group, substituted amino group, phenyl group, alkoxy group, ester group). Specifically, methoxy, ethoxy, isopropyloxy, benzyloxy, 2-hydroxyethoxy, carboxymethoxy, 2-carboxyethoxy, 2
Examples include groups such as -chloroethoxy and 2-methoxyethoxy.

The aryloxy group represented by R11 has 6 to 10 carbon atoms.
An aryloxy group is preferable, and a substituent is preferably an alkyl group having 1 to 4 carbon atoms in addition to a group that the alkoxy group represented by R2a described above may have.

).

Specifically, phenoxy, 4-methylphenoxy, 4-
Examples include groups such as carboxyphenoxy and 4-cyanophenoxy.

Examples of the halogen atom represented by R11 include fluorine, chlorine, and bromine.

Examples of the 5- or 6-membered ring formed by linking R12 and Rlt and/or R13 and R15 include a julolidine ring, a tetrahydroquinoline ring, and an indoline ring.

Examples of the 5- or 6-membered ring formed by linking Rlt and RI5 include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

The methine group represented by Lll, L12, and Lll represents a substituted or unsubstituted methine group. As the substituent, groups such as methyl, ethyl, phenyl, chlorine, and hydroxyethylcyano are preferable.

Preferred compounds in general formula (I) are those having at least one carboxyl group in the dye molecule.

Specific examples of the dye represented by the general formula (I) are listed below, but the present invention is not limited thereto.

■ ■ ■ ■-12 ■ ■ I3 ■ ■ ■ ■ ■ ■-22 ■ ■ ■ ■ ■ ■ ■ OOH ■ OOH OOH ■ ■ Cθ OOH ■ ■ OOH ■ OOH ■ OOH ■ CH2CH2C00H COOH COOH COOH COOH ■-46 0OH General The dye represented by formula (I) is disclosed in JP-A-4860918.
No. 51-128329.

Next, general formula (II) will be explained in detail.

R2 R22, R23, R21, R25, R26, R2
7, R2H, R30% The alkyl group represented by R31 or R3□ is preferably an alkyl group having 1 to 6 carbon atoms,
It may have a substituent (for example, fluorine, chlorine, hydroxyl group, carboxylic acid group, cyano group, substituted amino group, phenyl group, alkoxy group). Specifically, methyl, ethyl,
n-propyl, isopropyl, n-butyl, n-hexyl, hydroxyethyl, carboxyethyl, cyanethyl, methanesulfonamidoethyl, trifluoromethyl, benzyl, 4-carboxybenzyl, 2-methoxyethyl, 2-dimethylaminoethyl, etc. The following groups can be mentioned.

R21, R22, R2H, R2t, RIS, R2H, R
2□, R2g, RlOq The aryl group represented by R31 or R32 is preferably an aryl group having 6 to 10 carbon atoms, and a substituent (for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a carboxylic acid group, a sulfonamide group) , arylsulfamoyl group, halogen atom, cyano group, hydroxyl group). Specifically, phenyl, naphthyl,
4-carboxyphenyl, 3-carboxyphenyl, 3
, 5-dicarboxyphenyl, 4-hydroxyphenyl, 2-hydroxyphenyl, 3-methoxy-4-hydroxyphenyl, 4-methanesulfonamidophenyl, 4
Examples include groups such as benzenesulfonamidophenyl, 2,4-dicarboxyphenyl, 4-cyanophenyl, 4-ethoxycarbonylphenyl, and 2-methyl-4carboxydiphenyl.

L 21% The methine group represented by L 2□, L23 may have a substituent (for example, methyl, ethyl, chlorine, hydroxyethyl, cyano), and the methine groups are linked together to form a 5- or 6-membered rings (e.g. cyclopentene rings,
cyclohexene ring).

Preferred compounds in general formula (II) are R2+, R23, R
25 and R27 represent a phenyl group directly substituted with at least one carboxylic acid group or a phenyl group directly substituted with at least one sulfonamide group, and more preferably, all of the above conditions are met. It is something.

Below is the general formula Specific examples of dyes represented by R2+ J-6 II-4 OOH OOH ■ OOH OOH ■-5 OOH OOH ■ OOH OOH 0OH C00H OOH OOH ■ OOH OOH ■ OOH OOH ■ ■ C00H OOH OOH OOH ■ OOH OOH ■ ■ OOH OOH ■ OOH OOH ■ ■ OOH OOH ■ ■ H3 H3 ■ ■ OOH OOH ■ ] ■ OOH OOH ■ COOH OOH ■ OOH OOH ■-27 ■ ■ ■ CH2C82COOH CH2CH2COOH ■ CH3 OOH OOH ■ ■ ■ CH.

CH3 CH.

CH3 ■ ■ ■ 02CH3 SO□CH3 ■ ■ CH2CH20CH3 CH2CH20CH3 ■ CH.

CH3 ■ ■ ■ ■ 0OH COOI( ■ ■ General formula (II) The above specific example of the dye represented by home, What is preferably used in the present invention is ■ ■ 0～■ It is 42.

General formula (II) The dye represented by No. 92716, 63 No. 316853, Same 6 No. 40827, Special Publication No. 1983 35° No. 544 ]H It can be synthesized according to the method described in .

6. The compound of general formula (I) or (III) is used in an amount of 1 to 1000 mg per rn' of area on the light-sensitive material, preferably 1 to 800 mg per m'.

When using a compound of general formula (1) or (II) as a filter dye or antihalation dye, any effective amount can be used, but so long as the optical density is in the range of 0.05 to 3.5. It is preferable to use it.

The addition time may be any step before coating.

Solid fine particle dispersion of general formula (I) according to the present invention or (I
The solid fine particle dispersion I) can be used in either the emulsion layer or other hydrophilic colloid layer, and each dispersion may be used in the same layer or in separate layers.

Fine particle dispersions of compounds of general formula (I) or (II) according to the invention can be prepared by methods of precipitating the compounds of the invention in the form of dispersions and/or by known comminution means, e.g. A method of forming by ball milling (ball mill, vibratory ball mill, planetary ball mill, etc.), sand milling, colloid milling, jet milling, roller milling, etc. [In that case, a solvent (for example, water, alcohol, etc.) may be present.] It can be formed by Alternatively, after dissolving the compound of the present invention in a suitable solvent, a poor solvent for the compound of the present invention may be added to precipitate a microcrystalline powder. In that case, a dispersing surfactant may be used. good. Alternatively, the compound of the present invention may be first dissolved by controlling the pH, and then microcrystallized by changing the pH. The microcrystalline particles of the compound of the present invention in the dispersion have an average particle size of 10 μm or less, more preferably 2 μm or less, particularly preferably 0.5 μm or less. It is more preferable that the fine particles are 5 μm or less, and in some cases, 0.1 μm or less.

Gelatin is a typical hydrophilic colloid, but any other conventionally known hydrophilic colloids that can be used for photography can be used.

The silver halide emulsions used in the present invention are preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride.

The silver halide grains used in the present invention may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
ular) crystal form, or a composite form of these crystal forms. It is also possible to use a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms.

The silver halide grains used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase. Also, particles whose latent image is mainly formed on the surface (
For example, the emulsion may be a negative type emulsion), or it may be a grain mainly formed inside the grain (for example, an internal latent image type emulsion, a prefogged direct reversal type emulsion). Preferably,
These are particles on which a latent image is formed primarily on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5
It is a tabular grain emulsion in which grains having a diameter of 0.6 microns or less, preferably 0.3 microns or less, and an average aspect ratio of 5 or more occupy 50% or more of the total projected area. A monodispersed emulsion having the above coefficient of variation (value S/d obtained by dividing the standard deviation S by the diameter d in the distribution expressed by the diameter when the projected area is approximated as a circle) of 20% or less is preferable. Further, two or more types of tabular grain emulsions and porosity agents having a weight of 50 may be mixed.

The photographic emulsion used in the present invention is P.
, Glafkides), Chimie er Phys Photography (Chimie er Phys Photography)
ique Ph.

tographique) (published by Ballmontel, 1
967), G.F.Duffin (G.P. Du
ffin), Photographic Emulsion Chemistry (Ph.

tographic Emulsion Chemises
try) (Focal Press, 1966), V. L. Zelikman
) et al., Making and Coating Photographic Emulsions (Making and C
oating Photographic Emuls
ion) (Focal Press, 1964).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574, U.S. Pat. No. 628, No. 3,704,130, No. 4,297.439, No. 4,276.374, etc.), thione compounds (e.g., JP-A No. 144319/1983)
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.), etc. can be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., using various synthetic hydrophilic polymeric materials such as single or copolymers. I can do it.

In addition to general-purpose lime-processed gelatin, gelatin is acid-processed and the Japanese Society of Scientific Photography (Bull, Soc,
Sci, Phot, Japan), No. 1
Enzyme-treated gelatin may be used as described on page 6.30 (1966), or a hydrolyzate of gelatin may be used.

In the photographic material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active halogen compounds (2,4-dichloro-6-hydroxy-1,3° et al. 95-triazine and its sodium salt, etc.) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2 -bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether or a vinyl polymer having a vinylsulfonyl group in the side chain) are preferred because they quickly harden hydrophilic colloids such as ceratin and provide stable photographic properties. N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.) and haloamidinium salts (1-(1-chloro-1-pyridinomethylene)pyrrolidinium-2-naphthalenesulfonate, etc.) also have a slow curing rate. Faster and better.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nuclei, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbyl acid group can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds which are nitrogen-containing ring nuclei and are substituted (for example, U.S. Pat. Nos. 2,933,390 and 3,635°721)
(described in US Pat. No. 3,743,510), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3.615.613, U.S. Patent No. 3,6]
, No. 5,641, No. 3.617,295, No. 3,63
The combinations described in No. 5,721 are particularly useful.

The silver halide photographic emulsion used in the present invention contains the following ingredients for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or stabilizing photographic performance.
Various compounds can be included. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl 5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthion;
Azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1°3.3a
, 7) tetraazaindenes), pentaazaindenes, etc.; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, penscenesulfonic acid amide, etc. be able to.

The photosensitive material of the present invention contains one or more surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, and sensitization). But that's fine.

The photographic material prepared using the present invention may contain water-soluble dyes in the hydrophilic colloid layer as filter dyes or for various purposes such as anti-irradiation or anti-halation.

As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as necessary. A preferred layer arrangement is, from the support side, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in that order, a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer in that order, or a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer in that order. Further, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity.
The layer structure may further improve the graininess.

Furthermore, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. A configuration may also be adopted in which emulsion layers of different color sensitivity are inserted between emulsion layers of the same color sensitivity. A reflective layer made of fine grain silver halide or the like may be provided under the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve sensitivity.

Generally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. For example, it may be used in combination with an infrared-sensitive layer for pseudo-color image quality or semiconductor laser exposure.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like. The support surface is coated before or after priming.
Glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. may also be applied.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods can be used, such as dip coating, roller coating, curtain coating, and extrusion coating. U.S. Pat. No. 2,681,2 as appropriate.
No. 94, No. 2,761.791, No. 3,526,
Multiple layers may be applied simultaneously using coating methods such as those described in US Pat.

The present invention can be applied to various color and black and white photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, color reversal paper, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. can. Research Disclosure, No. 17123
(July 1978) or by utilizing a trichromatic coupler mixture as described in U.S. Patent No. 4,12 16.461 and British Pat. 1.02. 13
By using the black color-forming coupler described in No. 6, the present invention can also be applied to black-and-white photosensitive materials for X-rays and the like. Films for plate making such as lithography film or scanner film, X-ray film for direct/indirect medical use or industrial use, negative black and white film for photography, black and white photographic paper, C0
The present invention can also be applied to M-use or ordinary microfilms, silver salt diffusion transfer type photosensitive materials, and printout type photosensitive materials.

When the photographic element of the present invention is applied to color diffusion transfer photography, it may be of the peel-apart (beer-apart) type or
-16356, No. 48-33697, JP-A No. 5 (1973)
- integrated type as described in No. 13040 and British Patent No. 1,330,524;
It is possible to adopt a structure of a film unit that does not require peeling as described in JP-A-57-119345.

In either type of format described above, the use of a polymeric acid layer protected by a neutralizing timing layer is advantageous in increasing the processing temperature tolerance. When used in color diffusion transfer photography, it may be added to any layer in the sensitive material, or it may be sealed in a processing solution container as a developer component.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light, (sunlight), incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-burning flashbulbs are common.

Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, wires are used in microshutter arrays that utilize fluorescent screens (such as CRTs), liquid crystals (LCDs), and lanthanum-doped lead titanium zirconate (PLZT), which are emitted from phosphors excited by electron beams. It is also possible to use an exposure means that combines a shaped or planar light source. If necessary, the spectral distribution used for exposure can be adjusted using color filters.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, and 3-methyl- 4-amino-N-ethyl-Nβ
-Hydroxylethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromide iodides, benzimidazoles, benzothiazoles or mercapto compounds. It is common to include. Also, if necessary, preservatives such as hydroxylamines, dialkylhydroxylamines, hydrazines, triethanolamine, triethylenediamine or sulfites, organic solvents such as triethanolamine, diethylene glycol, benzyl alcohol, polyethylene glycol, etc. , quaternary ammonium salts, development accelerators such as amines, dye-forming couplers,
Competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, tackifying agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids West German patent applications for various chelating agents such as
OLS) No. 2,622,950 and the like may be added to the color developer.

In the development process for reversal color photosensitive materials, usually black-and-white development is performed, followed by color development. This black and white developer has
Known black and white developers such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol can be used in combination in a furnace that uses them alone. can.

In addition to a color developer, any photographic development method may be applied to the light-sensitive material of the present invention. The developing agents used in the developer include dihydroxybenzene-based developing agents, ■
- Phenyl-3-pyrazolidone type developing agents, p-aminophenol type developing agents, etc. These can be used singly or in combination (for example, l-phenyl-3-pyrazolidones and dihydroxybenzenes, or p-aminophenols and dihydroxybenzenes). ) can be used. Further, the light-sensitive material of the present invention may be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl pisulfite and hydroquinone.

In the above, examples of the dihydroxybenzene-based developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,
There are 3-dichlorohydroquinone, 2,5-dimethylhydroquinone, etc., and 1-phenyl-3-pyrazolidone type developing agents include 1-phenyl-3-pyrazolidone,
4.4-dimethyl-1-phenyl-3-pyrazolidone,
4-hydroxymethyl-4-methyl-1 phenyl-3-
Examples include pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, and p-aminophenol, N-methyl-p-aminophenol, etc. are used as the p-aminophenol developing agent.

A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, sodium formaldehyde bisulfite may be used, which provides almost no free sulfite ions in the developer.

As the alkaline agent for the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, jetanolamine, triethanolamine, etc. are used. The pH of the developer is usually set to 9 or higher, preferably 9.7 or higher.

The developer solution may also contain organic compounds known as antifoggants or development inhibitors. Examples include azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.: mercaptopyrimicins: mercaptotriazines, thioketo compounds such as oxazolinthione; azaindenes, For example, triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a.

7) Tetrazaindenes), pentaazaindene, etc.; benzenethiosulfonic acid, benzenesulfinic acid,
Examples include benzenesulfonic acid amide and sodium 2mercaptobenzimidazole-5-sulfonate.

The developer that can be used in the present invention may contain the same polyalkylene oxide as described above as a development inhibitor. For example, polyethylene oxide having a molecular weight of 1,000 to 10,000 can be contained in a range of 0.1 to 10 g/n.

It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraamine, hexaacetic acid, diethylenetetraamine pentaacetic acid, etc. as a water softener to the developer that can be used in the present invention.

The developer used in the present invention includes a compound described in JP-A No. 56-24347 as a silver stain prevention agent, a compound described in JP-A-62-212651 as an agent for preventing uneven development,
As a solubilizing agent, a compound described in JP-A-61267759 can be used.

In the developing solution used in the present invention, a buffering agent is used.
Boric acid described in No. 1-186259, JP-A-60-93
Saccharides (e.g., saccharose), oximes (e.g., acetoxime), phenols (e.g., 5-sulfosalicylic acid), tertiary phosphates (e.g., sodium salt, potassium salt), etc., described in No. 433 are used.

Various compounds may be used as the development accelerator used in the present invention (these compounds may be added to either the sensitive material or the processing solution).

Preferred development accelerators include amine compounds, imidazole compounds, imidacillin compounds, phosphonium compounds, sulfonium compounds, hydrazine compounds,
Examples include thioether compounds, thione compounds, certain mercapto compounds, isoion compounds, and thiocyanates.

This is especially necessary for rapid development processing in a short period of time. It is desirable to add these development accelerators to the color developing solution, but depending on the type of accelerator or the position on the support of the photosensitive layer to be accelerated, it may be added to the photosensitive material. can. It can also be added to both the color developing solution and the photosensitive material. Furthermore, depending on the case, a pre-bath for the color developing bath may be provided and the additive may be added therein.

Amino compounds useful as amino compounds include both inorganic amines and organic amines, such as hydroxylamine. Organic amines can be aliphatic amines, aromatic amines, cyclic amines, mixed aliphatic-aromatic amines or heterocyclic amines; primary, secondary and tertiary amines as well as quaternary ammonium compounds are all useful. be.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents include iron (■), cobalt (■), and chromium (■).
), compounds of polyvalent metals such as copper (II), peracids, quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I) or cobalt (I), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propatol tetraacetic acid; Complex salts of aminopolycarboxylic acids such as acetic acid or organic acids such as citric acid, tartaric acid, malic acid; persulfates; manganates;
Nitrone phenol and the like can be used. Among these, ethylenediaminetetraacetic acid iron(I) salt, diethylenetriaminepentaacetic acid iron(III) salt, and persulfate are preferable from the viewpoint of rapid processing and environmental pollution. Furthermore, ethylenediaminetetraacetic acid iron (I) complex salt is also used in a stand-alone bleach solution.
- Also particularly useful in bath bleach-fix solutions.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Patent No. 1,290.8.
No. 12, same 2. No. 059.988, JP-A-53-32
No. 736, No. 53-57831, No. 37418, No. 5365732, No. 53-72623, No. 5395
No. 630, No. 53-95631, No. 53104232
No. 5:3-124424, No. 53-141623
No. 5:3-28426, Research Disclosure No. 17129 (July 1978), etc. Compounds having a mercapto group or disulfide group; Thiazolidines as described in JP-A-50-140129 Derivatives: Thiourea derivatives described in Japanese Patent Publication No. 45-8506, Japanese Patent Application Laid-open Nos. 5220832 and 53-32735, and U.S. Patent No. 3,706,561; West German Patent No. 1. ．． No. 127,715, JP-A-58-1623
Iodides described in No. 5; polyethylene oxides described in West German Patent No. 966.410 and West German Patent No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others in Japanese Patent Publication No. 49-42434 , 49-5964
No. 4, No. 53-94927, No. 54-35727,
Compounds described in No. 55-26506 and No. 58-163940 and iodine and bromine ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat.
, 893,858, West German Patent No. 1,290,812, and JP-A-53-95630 are preferred. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioureas of thioether compounds, and a large amount of iodides, but thiosulfates are generally used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, fungicides and anti-piping agents that prevent the growth of various bacteria, algae, and mold. Agents, metal salts such as magnesium salts, aluminum salts, and bismuth salts, surfactants for preventing drying load and unevenness, and various hardening agents may be added as necessary. Or Photographic Science and Engineering by West (L, E, Wes
t, Phot, Sci, Eng,), Volume 6, 344
-359 pages (1965) etc. may be added. The addition of chelating agents and anti-piping agents is particularly effective.

In the washing process, two or more layers are generally washed in countercurrent water to conserve water. Furthermore, instead of the water washing process,
A multi-stage countercurrent stabilization treatment process such as that described in No.-8543 may be implemented. In the case of this step, 2 to 9 countercurrent columns are required. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, the membrane p
Various buffers for adjusting H (e.g. pH 3-9) (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sulfur hydroxide, ammonia Typical examples include aldehydes such as formalin (used in combination with water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolysulfonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (benzisothiazolinone, irithiazolone, 4-thiazoline, etc.) are added as necessary. Various additives such as benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners, etc. may be used, and two or more compounds for the same or different purposes may be used. May be used together.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

Furthermore, in the case of color sensitive materials for photography, the normally performed post-fixing (washing-stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water-saving treatment). At this time, if the amount of magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

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

For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342,599, Research Disclosure No. 14850 and US Pat. No. 15159
In addition to the Schiff base type compounds described in No. 13924, the andole compounds described in U.S. Pat. No. 13924, the metal salt complexes described in U.S. Pat. No. 56-6235, No. 56-16133, No. 56-59232, No. 5
No. 6-67842, No. 56-83734, No. 56-8
No. 3735, No. 56-83736, No. 56-8973
No. 5, No. 56-81837, No. 56-54430,
Examples include various salt-type precursors described in No. 56-106241, No. 56-107236, No. 57-97531, and No. 57-83565.

The silver halide color photosensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are JP-A Nos. 56-64339, 57-144547, 57-211147, 58-50532, 58-50536, 58-50533, and 58-
No. 50534, No. 58-50535 and No. 58-■
It is described in No. 15438, etc.

Various processing liquids in the present invention are used at LO'C to 50'C. A temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. I can do it. Furthermore, for the purpose of improving the stability of photosensitive materials, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2.226.770 or US Pat. No. 3,674.499 may be carried out.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

When the light-sensitive material of the present invention is a color paper, it can be generally subjected to a whitening fixing process, and even when it is a color photographic material for photographing, it can be subjected to whitening fixing treatment as necessary.

(Effects of the Invention) In the silver halide photographic light-sensitive material of the present invention, the dye in the dye layer has appropriate spectral absorption and has an excellent effect of selectively dyeing the dye layer and not diffusing to other layers. .

The silver halide photographic material containing the compound of the present invention is easily decolorized or eluted by photographic processing, provides a low Dmin, does not reduce sensitivity, and has the effect that there is little decrease in sensitivity due to storage.

Further, the silver halide photographic material of the present invention provides images with improved sharpness. Furthermore, photographs obtained from the silver halide photographic material of the present invention do not produce staining, are stable even during long-term storage, and do not deteriorate in photographic performance.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 (Preparation of Emulsion A) A silver nitrate aqueous solution and a sodium chloride aqueous solution containing 0.5 x 10 mol of ammonium hexachloride rhodium(I) per mol of silver were brought to pH 6 in a gelatin solution at 35°C by a double jet method. A monodispersed silver chloride emulsion with an average grain size of 0.07 μm was prepared by mixing while controlling the grain size so that the grain size was 0.07 μm.

After particle formation, soluble salts are removed by flocculation methods well known in the art, and stabilizers 4-hydroxy-6-methyl-1,3°3a, 7-tetraazaindene and 1-phenyl- 5-mercaptotetrazole was added. 1 kg of emulsion contained 55 g of gelatin and 1 kg of silver contained 105 g. (Emulsion A) (Preparation of photosensitive material) Add the following nucleating agent and nucleation accelerator to the emulsion A,
Next, polyethyl acrylate latex (300mg
/m), 2,4 dichloro-6-hydroxy 1,3.5-triazine sodium salt was added as a hardening agent, and polyethylene terephthalate was added so that the amount of silver was 3.5 g per 1 m. Amount (mg/proof) I - A silver halide emulsion layer was coated on the upper transparent support, and gelatin (1.3 g/m) and compound I-35 of the present invention (0.1 g/rri') were added to the upper layer. ), a protective layer containing the following three surfactants, stabilizers, and matting agents as coating aids was applied and dried.

(Sample 1) Surfactant Addition amount (mg/po) Stabilizer thioctic acid 6.0 Matting agent polymethyl methacrylate (average particle size 2.5μ) 9.0 Compound ■-35 of the present invention was prepared using the following procedure. A dispersion was prepared and used.

(Preparation of dye dispersion) ■Liquid CH2C00C,H,.

CHCOOC,H,3 SO+Na 7 g of solution (2) While stirring solution (2) at 40°C, solution (2) was added little by little.

(Preparation of comparative sample) ■) In Example 1, the following dye was used instead of compound ■-35, and water 537 was used instead of dimethylformamide in solution ■.
A sample was created using nl (comparative sample 1-A
). This dye is exemplified in Japanese Patent Publication No. 48-3286.

3) Comparative sample 1-C was prepared using the following protective layer in place of the protective layer containing compound 1-35 of the present invention in Example-1.

C00CH2CH2NH(C2H5)2-CAe dye 0.75g/po(0,075g/rrr) 2) In Example 1, the following dye was used in place of compound 1-35. (Comparative Sample 1-B) This dye is exemplified in JP-A-63-197943.

CH3 0゜1g/posurfactant C,,823CONH(CH2)3N(CH3)2(C
H2) tso, θ0゜53g/a CH2C00C6H CHCOOC, H 0゜S O3N a C3H7 Stabilizer thioctic acid 0.006 Matting agent polymethyl methacrylate (average particle size 2.5μ) 0.009 (performance evaluation) (1) The above four samples were exposed to light through an optical wedge using a Dainippon Screen ■ Meisho printer P-607, developed with the following developer at 38° C. for 20 seconds, fixed in a conventional manner, washed with water, and dried.

Basic recipe for developer Hydroquinone 35.0g N-methyl-P-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 13.0g Potassium triphosphate 74. 0g potassium sulfite
90.0g ethylenediaminetetraacetic acid tetrasodium salt 1.0g potassium bromide 4.0g 5-methylbenzotriazole 0.6g 3-diethylamino-1,
2 Add 15.0g of propanediol water
11 (pH=11.5) As a result, Example 1 and comparative samples 1-A and 1-C
was completely bleached, but comparative sample IB remained with a yellow stain. Comparative sample 1-B has a development time of 3
When the time was increased to 0 seconds, the color was completely decolored. As described above, the compounds of the present invention are rapidly processed and decolorized.

(2) Test of Tone Variability The above five samples were exposed to light through a flat mesh screen using the above printer, and were otherwise developed in the same manner as in the test (1). After determining the exposure time for each sample to return the halftone dot area to 1.I, perform exposure for twice and four times that exposure time to see how much the halftone dot area has expanded. I investigated whether The larger the enlargement, the better the tone variability. The results are shown in Table-1. As can be seen from Table 1, Comparative Sample 1-A has a significantly reduced tone variability, whereas Sample 1 of the present invention has a high tone variability. This is because the dye used in comparative sample 1-A is water-soluble and diffusible, so it is uniformly diffused from the added layer to the light-sensitive emulsion layer during storage, even if the exposure time is increased. This is because the expansion of the halftone dot area was suppressed due to the irradiation prevention effect of the dye. On the other hand, the compound I-1 of the present invention exhibits high tone variability since it is fixed in the added layer.

Comparative samples 1-B and 1-C also showed good tone variability.

Table 1: Tone variability (indicated by increase in halftone dot area) (3) Evaluation of contamination by reducing fluid (stain) Strips of samples of the present invention and comparative samples obtained by processing in (2) above was immersed in the following Farmer's reducing solution at 20°C for 60 seconds, washed with water, and dried. As a result, the dot area of each sample was reduced to about 33% at 50%.
In comparison sample 1-C, intense brown staining occurred over the entire surface. No stain was observed in the samples of the present invention and comparative samples 1-A and IB.

farmer reducer liquid 1st liquid: 2nd liquid: water during use 100 copies = 5 copies = 100 copies Mix with

As described above, the samples of the present invention had good decolorization properties, tone changeability, and force reduction properties.

Example 2 1 Ringuchi] Preparation of dye fixing layer (antihalation layer) Dye -
4 were ball milled using the method described in JP-A No. 63-197943.

4347 nl of water and 6.7% aqueous solution of Triton X-200R surfactant (TX-200R) 791-
and was placed in a 2β ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 400i (2 mm diameter) were added and the contents were ground for 5 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. When the obtained dye dispersion was observed, the average particle size of the pulverized dye was 0.43 μm.

A transparent PET support with a thickness of 100 μm was used as the support. In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support was previously subjected to corona discharge treatment, and then a first undercoat layer made of styrene-butadiene latex was applied, and a second undercoat layer of 0.08 g/rd of gelatin was applied on top of the first undercoat layer. An undercoat layer was provided.

A fine dispersion of the dye was coated on this support as a gelatin dispersion solution in the coating amount shown below. In this way, an antihalation layer was prepared.

・Ceratin・Dye I-4 ・Polystyrene sulfonic acid strength (average molecular weight 600,000) 1.8 g/n (amount listed in Table 1 35 mg/m ・Phenoxyethanol 18 mg/r&・1
, 2-bis(vinylsulfonylacetamido)ethane 100mg/Preparation of anti-emulsion coating solution Raw milk #1 shown below is a surface latent image type emulsion, and negative-tone characteristics can be obtained using a commercially available microfilm general-purpose processing solution. That's what you get. Furthermore, by performing reversal processing using a reversal processing liquid, positive type characteristics can be obtained.

<Preparation of raw emulsion #1> Solution I 75°C Solution III 35°C Solution m 35°C Solution ■ Solution ■ and solution ■ were added simultaneously over 45 minutes to solution 1 that had been well stirred at room temperature, and the total amount At the end of the addition, a cubic monodisperse emulsion with an average grain size of 0.28 μm was finally obtained.

At this time, the addition rate of solution (1) was adjusted with respect to the addition of solution H so that the pAg value in the mixing container was always 7.50. Note that solution (2) was added over a period of 5 minutes starting 7 minutes after the start of addition of solution (2). After the addition of solution ■ is complete,
After washing with water and desalting by the sedimentation method, inert gelatin 10
It was dispersed in an aqueous solution containing 0 g. To this emulsion were added 3 each of sodium lithiosulfate and chloroauric acid tetrahydrate per mole of silver.
After adding 4 mg each and adjusting the p)J and I)Ag values to 8°9 and 7.0 (400C), respectively, chemical sensitization was performed at 75°C for 60 minutes to form a surface latent image type halogen. A silver emulsion was obtained. The layer structure and the composition of each layer are as follows.

Layer structure Film thickness (μm) <Emulsion layer> Sample 1 was obtained by preparing and coating each component in the emulsion layers other than the antihalation layer, the surface protective layer, the conductive layer, and the Ge1 layer in the following coating amounts.

<Protective layer> Rium <Ge1 layer> Coating amount mg/m Sensitizing dye (compound ■) C2H.

(CH2)3SO8e <Back conductive layer> C2H.

Samples 2 to 10 were prepared in the same manner as Sample 1, except that dyes listed in Table 1 were used in place of Dye 4 used in the dye fixed layer in Sample 1. For comparison, Sample 11 was also prepared in which only dye I-4 was removed from Sample 1.

Each of the obtained samples was subjected to the following treatments and evaluations.

``Gen'' L Denpo ■ Reversal development processing Reversal development processing was performed using a commercially available reversal processing solution (FR-531, manufactured by FR Chemicals, Inc., USA) using an F10R reversal deep tank automatic developing machine manufactured by A11en Products, Inc.
, 532, 533, 534, 535) under the following conditions.

■Negative development processing Negative development processing is carried out using a commercially available general-purpose microfilm processing solution (F R Chemicals, Inc., USA) using an F10 deep tank automatic developing machine manufactured by A11en products in the United States.
R-537 developer) under the following conditions.

■Evaluation of sharpness Sharpness was evaluated using MTF. The photographic material was exposed to white light for 1/100 seconds using an MTF measurement wedge and processed in an automatic processor as described above.

The MTF was measured using a 400×2μ aperture, and an optical density of 1.0 was measured using an MTF value with a spatial frequency of 20 cycles/mm. Evaluation was made in the 0 part.

The results are shown in Table-1.

(2) Evaluation of residual color After the unexposed film was subjected to the automatic development process described above, the green transmission density and blue transmission density were measured through a Macbeth Status A filter.

(*) The combination of comparative dyes 1) and 2) is JP-A-63-1
The following dyes are exemplified in No. 97943.

(2) It can be seen that according to the present invention, a silver halogen photographic light-sensitive material with high sharpness and little residual color can be obtained.

Claims (2)

[Claims] (1) A silver halide photographic material comprising a hydrophilic colloid layer containing a solid fine particle dispersion of a dye represented by the following general formula (I). (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Q_1_1 forms a 1,3-indanedione ring, an isoxazolone ring, a 2,4-oxazolidinedione ring, a barbituric acid ring, or a thiobarbituric acid ring. Represents a group of nonmetallic atoms necessary to R_1_1 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, a halogen atom, or a cyano group. R_1_2 and R_1_3 each represent a hydrogen atom, R_1_2 together with R_1_4, or R_1_3 together with R_1_5 each represent a group of nonmetallic atoms necessary to form a 5- or 6-membered ring. R_1_4 and R_1_5 each represent an alkyl group or an aryl group, or R_1_4 and R_1_5 may form a 5- or 6-membered ring together. L_1_1, L_1
_2, L_1_3 represent methine group, n_1_1 is 0
, 1 or 2. (2) It is characterized by containing a fixed fine particle dispersion of a dye represented by the general formula (I) described in claim 1 and a solid fine particle dispersion of a dye represented by the following general formula (II). A silver halide photographic material according to claim 1. (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Q_2_1= represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and -Q_2_2 means ▲Mathematical formula, There are chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R_2_1 and R_2_5 each represent a hydrogen atom, an alkyl group, or an aryl group,
, R_2_4, R_2_6, R_2_8 are an alkyl group, an aryl group, OR_3_0, COOR_3_0,
NR_3_0R_3_1, CONR_3_0R_3_1
,NR_3_0COR_3_2,COR_3_2,NR
_3_0CONR_3_0R_3_1, SO_2R_3
_2 or a cyano group, and R_2_3 and R_2_7 represent a hydrogen atom, an alkyl group, an aryl group, COR_3_2 or SO_2R_3_2. However, R_3_0, R
_3_1 each represents a hydrogen atom, an alkyl group or an aryl group, and R_3_2 represents an alkyl group or an aryl group. ), L_2_1, L_2_2, L_2_3 each represent a methine group, and n_2_1 represents 0, 1 or 2. ]