JPH02282244A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make it possible to dye only a prescribed layer of a sensitive material and to accelerate decoloring and/or leaching in development by using a specified compd. CONSTITUTION:A hydrophilic colloidal layer contg. dispersed fine particles of a compd. represented by the formula is formed in the sensitive material. In the formula, R1 is H, alkyl, etc., R2 is H, alkyl, etc., R3 is H, cyano, etc., each of L1-L3 is methine and n is 0-2. It is preferable that the compd. is practically insoluble in water at pH<=6 but soluble in water at pH>=8 and is free from a sulfonic acid group (salt) or a carboxylic acid group (salt) as a substituent. When the compd. is used in an antihalation layer, a sensitive material preventing the lowering of the sensitivity, fog and the remaining of color after processing and hardly leaving silver is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material having dyed columns and an aqueous colloid layer, which is photochemically inert and easily processed during photographic processing. The present invention relates to a silver halide photographic photosensitive material having a hydrophilic colloid layer entirely containing a solid*particle dispersion of a dye to be decolorized and/or eluted.

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

Spectral composition of light that should be incident on the photographic emulsion layer! 2. When total control is required, the colored layer is usually placed 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. Blurredness or halation? For the purpose of preventing this, a colored layer called a VC prevention layer is provided between the photographic emulsion layer and the support, or on the opposite side of the support from the photographic emulsion layer. When there are multiple photographic emulsion layers, an antihalation layer may be placed between the layers.

Due to the scattering of light in the photographic emulsion layer (reduction in image sharpness (this phenomenon is generally called irradiation))
In order to prevent this, the photographic emulsion layer may be colored.

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

(1) Appropriate total 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.

Many proposals have been made to find dyes that meet the above conditions. For example, the oginnol dye having a pyrazolopyridine nucleus described in Jikai Shoyu 2-/3333.5', No. 63-271r31 is the one described in (1), (2), (3) above.
It satisfies the conditions (5) and has excellent rutting properties as an irradiation-preventing dye.

However, especially 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 rest are It is often necessary to prevent coloring from reaching the layer, and the condition (4) above becomes a heavy burden. This is because, otherwise, not only will it have harmful spectral effects on other layers, but its effectiveness as a filter layer or antihalation layer will be diminished. Therefore, the above-mentioned oquinol dyes having a pyrazolopyridine nucleus were not necessarily sufficient for the above condition (4). Much effort has been made in the past to prevent such dye diffusion.

For example, a method in which a hydrophilic polymer with a charge opposite to that of a dissociated anionic dye is made to coexist in a layer as a mordant and the dye is localized in a specific layer by interaction with dye molecules is disclosed in the US patent. ≠Do.

5t≠ issue, same number, 7.2 Hiro, 3tt issue, same number 3,625,
It is disclosed in G Rihiro issue etc.

In addition, a method of dyeing a specific color using a solid dye in water is described in Japanese Patent Application Laid-Open No. 56-/λz3, No. 27 of the same publication.
No. 16, same Tatar/663ri No. 0, same! r-/j! 3r
/ issue, 63-271r31, 63-tri 75> Ko 3, European special plan 1st evening, t.

No. 1, same, 27≠, No. 723, same 2761 Taro 6@, same 2Y? , 443! No., U.S.%FFf'I,I0
3, No. 30, National Exemption Application Publication (WO), 1'
It is disclosed in Ilo Hiromu 75' g, etc.

1. A method of dyeing a specific layer using fine metal salt particles with dye adsorbed is described in US Pat.
Same 2. '1-9t, lll-/issue, same 2. Geta 6゜l!
'≠3, JP-A-60-GJ237, etc.

X - However, even with these improved methods,
Due to the slow decolorization and/or elution rate of dyes during development processing, it is necessary to speed up the processing, improve the processing solution composition, or
When there are changes in various factors such as improvements in the emulsion composition, it is difficult to eliminate residual color staining caused by dyes.

[Problem to be solved by the invention]

Therefore, it is an object of the present invention to provide a photographic material in which a dye in the form of a solid fine particle dispersion is used, which selectively images only a specific layer in a photographic light-sensitive material, and which quickly decolorizes and/or dissolves into a photographic material. The purpose of the present invention is to provide photosensitive materials.

[Failure to solve the problem]

As a result of various tests carried out by the present inventors, the object of the present invention is to provide a silver halide photographic photosensitive material characterized by having a hydrophilic colloid layer containing a solid fine particle dispersion of a compound represented by the following formula (I): We have discovered what can be achieved with materials.

General formula (1) [wherein R1 represents a hydrogen atom, an alkyl group, or an aryl-blocking ring group, and R2 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, C0R4 or 5OzR4,
R3 is a hydrogen atom, /ano group, hydroxyl group, carboxylic acid group, alkyl group, aryl group, COOR4, OR4, Nt(5
'R6, C0NR5R6IN1. L5cott,,NR
55O2Et4 or NR5CON R5,R6 (here, R4 represents all alkyl groups or aryl groups, R5, R
6 represents a hydrogen atom, an alkyl group or an aryl group. )
, L], R2, R3 or each represents methine Mf, and n represents 0 and/or 2. ] The compound represented by the general formula (1) of the present invention is pttg
It is preferable that it is substantially water-insoluble below and is water-insoluble above phir.

Further, it is particularly preferable that the compound represented by the general formula (1) of the present invention does not have a sulfonic acid group or a salt thereof or a salt of a carboxylic acid group.

The compound represented by general formula (I) will be explained in detail below.

The alkyl group represented by R1, R2, [(, 3, R4, [(5 and R6) is an alkyl group having 1 to 1.2 carbon atoms (
For example, methyl, ethyl, n-propyl, n-7thyl,
n-hexyl, n-tecyl, isopropyl, isobutyl, t-butyl), and substituents [e.g., hydroxyl group, carbonic acid group, noano group, nitro group, halogen atom (e.g., chlorine, bromine, fluorine), Alkoxy groups (e.g. metquin, ethquin), aryl groups (e.g. phenyl,
p-Calphokidiphenyl, p-hydroxyphenyl, p
-methylsulfamoylphenyl), amino groups (e.g., methylamino, diethylamino), acylamino groups (e.g., acetylamine, benzoylamino), sulfonamide groups (e.g., dj, ivy, tansulfonamide, benzenesulfonamide) , carbamoyl MKC (eg methylcarbamoyl, ethylcarbamoyl, phenylcarbamoyl), sulfamoyl group (eg methylsulfamoyl, phenylsulfamoyl)).

The aryl group represented by R, R2, R3, R4, R5 or R6 represents a phenyl group or a naphthyl group, and a substituent [tlJ, such as a hydroxyl group, a carboxyl group, a sulfonamide group (for example, methanesulfonamide, benzenesulfonamide) ), acylamino groups (e.g. acetylamino, piparoylamino, benzoylamino), sulfamoyl groups (reportedly methylsulfamoyl, ethylsulfamoyl, phenylsulfamoyl), carbamoyl groups (e.g. methylcarbamoyl, ethylcarbamoyl, phenylcarbamoyl), ureido group (e.g. 3-
methylureido, 3-(p-carboxyphenyl)ureido), cyano group, nitro group, halogen atom (for example,
chlorine, chlorine, fluorine), alkyl groups (e.g. methyl,
ethyl, n-propyl, t-butyl, isopropyl),
Alkoxy groups (e.g., methoxy, ethoxyno), ester groups (e.g., carbonyl, carbonyl, acetyloquine), amino groups (e.g., dimethylamino, diethylamino))'t? rl.

You can leave it there.

1, (represented by 1, R2) is at least 1
- or Z-membered nitrogen-containing heterocyclic groups having 3 nitrogen atoms (e.g., pyridin-λ-yl, quinolino-!-yl, benzothiazol-2-yl, benzoxazol-2-yl, pyrimidin-2-yl) is represented by a substituent [e.g., carboxy group, hydroxyl group, sulfonamide group (e.g.,
benzenesulfonamide, methanesulfonamide), anruami/M (for example, benzoylamino, p-cyanobenzoylamino)].

The methine group represented by Ll, R2 or R3 includes not only an unsubstituted methine group but also those having a substituent (for example, methyl, ethyl, benzyl, phenyl, carboxylic acid, /ano, fluorine, chlorine) and methine groups. include.

Preferred among the general formula (I), phenyl in which at least one of R1 or R2 has at least 7 groups selected from the group consisting of a carboxylic acid group, a sulfonamide group, a sulfamoyl group, or a hydroxy group. ^(, represents an aralkyl group or an alkyl group. 1-1, or 1-
Preferred examples of t2 include p-carboxymphenyl group,
n-carboxyphenyl group, 0-carboxyphenyl group, 31-terdicarboxyphenyl group, 21≠-dicarboxyphenyl moiety 1.2, t-carboxyphenyl &, I)-hydroquinphenyl A! , p-methanesulfonamidophenyl group, p-benzenesulfonamidophenyl group, m-benzenesulfonamidophenyl &, p
-(N-ethylsulfamoyl)phenyl M, p-(N
-phenylsulfamoyl) phenyl group, p-carboxyphenyl group, m-carboxybenzyl group, 0-carboxybenzyl group, p-carboxyphenethyl group, 2. 'I
-Dicarboxy 7 benzyl group, cocarboxy/ethyl 4%
, 3-carboxypropyl group, carboxinmethyl group, p
-Hydroxybenzyl i,o-(N-methylsulfamoyl)benzyl group may be mentioned.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

Specific examples (1-/) to (1-37) are shown in a form that specifically represents the replacement fund of - formation (I).

/ 3 The dye represented by the general formula (1) is, for example,
2. 20t No. ≠ 3-3 evening Ol/ No. J No. 310
Yuwo No., Mukai 31'-31/Zri No., same! rjf-100
Tata issue, same Ta♂-3 evening≠ issue, JP-A show t7-27 Otsu λ
It can be synthesized by using all the methods described in No. θ, No. 3i, No. 63-3/1lrE, and US Pat.

Synthesis example 1 (synthesis of compound 1-3) Goomethyl-7-hytroquinethyl, 2-(II.

carboquinphenyl) bilasoro[3,ti-b]birin-31 names-dio76.3g1 malonaldehyde cyanyl λ, 2i, triethylamineco.

r Punishment, methanol, 20ml 1. Acetic anhydride! After stirring the mixture of 100 g and 100 g for 10 hours at ￥ temperature, 200 g of acetic acid was added thereto, and the mixture was further stirred for 1 hour on an IHJ. All the precipitated crystals were collected. After dissolving the obtained crystals in N-dimethylformamide, ethanol was added and the resulting precipitate was collected to obtain the compound (-3) as a blue powder.
Obtained. 2m21X= lr j 6 nm (methanol containing triethylamine (2%)) Synthesis example 2 (compound l
Synthesis of -1) ≠, 7-dimethyl-co(≠-carboxyphenyl)pyrazolo(3,lLt, b)pyridine-3,-dione z
, /9. Glutaconaldehyde cyanyl m salt,',
'9, ethylamine 71, anhydrous F@, 2.
A mixture of 30 ml of N-dimethylformamide was stirred at room temperature in the evening. Bi I in the reaction solution: @tomi:
After washing with eggs and stirring for 1 hour, the precipitated crystals were counted. After dissolving the obtained crystals in N-dimethylformamide, isopropylene and o-nonyl were added and the resulting precipitate was evaporated at ℃ to obtain 0.7 g of l-A''k dark blue powder. λmax=7j, znm (triethylamine (2%)
In general, the compound of general formula (1) has an area/m on a photosensitive material.
Approximately 1 to 1000 TL9 is used per serving. Conveniently,
It is about 7m2 and a half/~goo■.

When using the compound represented by the general formula (1) as a filter dye or antino-rayon dye, any effective range can be used, but the optical density is in the range of 0.0 to 3. It is preferable to use it in such a way that it can be added.It can be added at any stage before coating.

The compound of general formula (I) according to the present invention can be used in both emulsion layers and other hydrophilic colloid layers.

The fine particle dispersion of the compound of general formula (1) of the present invention can be prepared by a method of completely precipitating the uninvented compound in the form of a dispersion, and/or by a known pulverization method such as ball milling in the presence of a dispersant. A method of forming temperature by sand milling, colloid milling, jet milling, roller milling, etc. (ball mill, vibrating ball mill, planetary ball mill, etc.) (in that case, a solvent (e.g. water, alcohol, etc.) may be coexisting (but Alternatively, after dissolving the compound of the present invention in a suitable solvent, the entire poor solvent for the compound may be added to 1 of the present invention to precipitate a microcrystalline powder. In that case, a dispersing surfactant may be used.

, 20- Alternatively, by controlling the compound ip E-1 of the present invention, it may be first dissolved and then microcrystallized with pt (total change).

The fine particles of the compound of the present invention in the dispersion have an average particle size of 10
2 μm or less is more preferable than 0.0 μm or less. It is less than 1 μm, and in some cases 0.7 μm.
The following fine particles are more preferable.

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

The silver halide emulsion and light-sensitive material used in the silver halide photographic light-sensitive material of the present invention will be described in detail.

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 spheroid or plate.
gular) crystal form, certain -, 2/-, or a composite form of these crystal forms.

Although it is possible to use a mixture of particles of various crystalline shapes, it is preferred to use all regular crystalline forms.

The silver rodanide grains used in the present invention may have different phases inside and on the surface, and may be uniformly composed of a C phase. Also, grains in which the latent image is mainly formed on the top surface (for example, negative emulsion) may be used, or grains in which the latent image is mainly formed inside the grain (for example, internal latent image emulsion, direct reversal emulsion with pre-fogged ). Preferably, the particles are such that latent images are formed mainly on six sides.

The silver halide emulsion used in the present invention has a thickness of 0.85 mm.
A tabular grain emulsion in which grains having a diameter of 0.3 microns or less, preferably 0.3 microns or more, and an average density ratio of 5 or more occupy 0% or more of the total projected area. Or, a monodispersed emulsion with a statistical coefficient of variation (S/d, the value obtained by dividing the standard deviation S by the diameter d in a distribution where the projected area is approximated by the diameter of a circle) of 20% or less. is preferred. Further, one or more types of tabular grain emulsions and monodispersed emulsions may be mixed.

The photographic emulsion used in the present invention is P.
, 01afkides), Shimmy Physique Photographic (Ch+m+e erPhy
sique photographeque) (Bolco 2 Montell Publishing, /riz7), G.F. Tuffin (
G., F. Duffin), 77+-Thornfick
Emulsion, Chemistry (Photo.

graphic emulsion chemist
y) (published by 7 Orcal Press, 1999), written by V, L, Zelikman et al., Meking & Coating Photographic F /I/Ji=+n (Making and C
oatingPhotographic Emulsi
It can be prepared using the method described in ``On)'' (7 Orcal Press, / Hirotoshi Riotoshi).

In addition, this halogenation; when silver grains are formed, in order to control the growth of grains, silver rhodide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (e.g., U.S. Pat. No. 3, 27, 137
No. j, 4741-, 4.2.1', No. 3, 7
04t, No. 730, No. 1, No. 7, No. 3, No. 1, No.
, 27! , 37≠, etc.), thione compounds (for example, JP-A-ShojJ-/Ko1.t3/ri, J3-♂, 21A
Og issue, same number 3! -77737 etc.), amine compounds (
For example, JP-A-Sho TG-IO.

7) 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/or other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfur esters, sugar derivatives such as alginic soda, and starch derivatives. ; Various synthetic highly hydrophilic materials such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc.; Molecular substances can be used.

As for gelatin, in addition to general-purpose lime-processed gelatin, lime-processed gelatin and the journal of the Japanese Society of Scientific Photography (BullSoc, S
ci, Photo, Japan), A/Otsu, 30 pages (/
Enzyme-treated gelatin as described in <+) may be used, and a gelatin hydrolyzate may also be used.

In the photosensitive material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic photosensitive layer or the pack layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active halogen compound (J, 4t-dichloro-2-hydroxy-/,
3゜1-triazine and its sodium salt, etc.) and active vinyl compounds (/13-bisvinylnulfonyl!)
-Furopanur, /12-bis(hinylsulfonylacetamido]ethane, bis(vinylsulfonylmethyl)ether, vinyl polymers with vinylsulfonyl groups in the side chain, etc.) can quickly harden hydrophilic colloids such as gelatin, resulting in stable photographs. It is preferable because it gives characteristics. N
-Carbamoylpyridinium salts ((/-morpholinocarbonyl-3-pyrinnio)methanenulphonate, etc.)
and haloamidinium salts (/-(/-chloro-7-pyridinomethylene) pyrrolidinium 2-naphthalene nulphonate, etc.) are also excellent in their fast curing speed.

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 melonanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes and hemioquinol 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.; a nucleus 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, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, penzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazoline-yone nucleus, a thiohydantoin nucleus, a monothioxazolidine-2,
3-t such as '/--dione nucleus, thiazolidine-,2,4Z-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc.
A two-membered heteroartic ring nucleus 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, aminostilbenzene compounds which are nitrogen-containing heteroartic ring nuclei groups and are substituted (for example, U.S. Pat.
2/), aromatic organic acid formaldehyde condensates (for example, those described in US Patent No. 3.74t, g, tio), cadmium salts, azaindene compounds, and the like. For US patents 3. l+/j, No. 613, 43. t/J, A'l1, same 3. AI7,293, 3. t3. Particularly useful are the combinations described in No. t, No. 7.2Z.

The silver halide photographic emulsion used in this technology contains various compounds for the purpose of preventing fogging during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance. be able to. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitroindimidazoles, chlorobenzimidacyls, bromobenzimidazoles, norcaftothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles. mercaptopyrimidines: mercaptopyrimidines; thioketo compounds such as oxadolinthion such as triazaindenes, tetraazaindenes (particularly hydroxy-substituted (/)).

3.3a, 7) Tetraazaindenes etc.; Adding many compounds known as anti-capri agents or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide etc. I can do it.

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.

Photographic materials made using the present invention may contain water-soluble dyes in the hydrophilic colloid layer as filter dyes or for induction or antihalation and other moderate purposes.

As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, anine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. It is. 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 λ 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.

A non-light sensitive layer may also be present between one or more emulsion layers having the same color sensitivity. A structure may be adopted in which emulsion layers with different color sensitivities are inserted between emulsion layers with the same color sensitivities.A reflective layer such as fine-grain silver rhodanide is provided below the high-sensitivity layer, especially the high-sensitivity blue-sensitive layer. may be provided 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, an infrared-sensitive layer may be combined to provide 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. Examples of useful flexible supports include nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, and polyvinyl chloride.
A film made of a semi-synthetic or synthetic polymer such as polyethylene tere-7-thalerate or polycarbonate, a baryta layer, or paper coated or laminated with an α-olefin polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), etc. are used.

The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The raw surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like. Support 6 times 1 time before or after priming treatment
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. Patent No. KO♂/-22 as necessary
≠ No. 27 Otsu/7ri No. 7, No. 27, ? ,t,2&4
．． 2g issue and 330g issue? Multiple layers may be applied simultaneously by the coating method described in ≠No. 7 and the like.

The present invention can be applied to various color and black and white photosensitive materials. Color negative film for general use or motion pictures, color reversal film for slides or television, one part for color, one part for color positive film and one part for color reversal, color diffusion transfer type photosensitive materials, heat developable color photosensitive materials, etc. This can be cited as an example. Research Disclosure, A/7/2J
(/27g, July 2013), or by using the tricolor coupler mixture described in U.S. Patent No. ≠, /,? B,
X
Kineimei can also be applied to black-and-white photosensitive materials such as those for line printing. This book also includes plate-making films such as lithography film or scanner film, direct, indirect medical or industrial X-ray film, negative black and white film for photography, black and white photographic paper, COM or regular microfilm, and printout type photosensitive materials. The invention can be applied.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits a total amount of radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or blocking light source. Natural light (sunlight), incandescent electric lamps, halogen-filled lamps, mercury lamps, fluorescent lamps, and
Flash light sources such as wood or metal-burning flash pulp are common.

Gas, dye or semiconductor racers, 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, micro-shutters using fluorescent light emitted from phosphors excited by electrons (CRT, etc.), liquids (LCI)), lanthanum-doped lead titanium zirconate (PLZT), etc. Exposure means in which an array is combined with a linear or planar light source can also be used. If necessary, the spectral distribution used for exposure can be adjusted by using a color filter.

The color developing solution used in the development of the light-sensitive material of the present invention is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, but p-phinidine diamine compounds are preferably used. 3-Methyl-≠-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-≠-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-7-amino-N-ethyl-N
-4-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-toluenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer contains pn buffers such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromides, iodides, benzimidazoles, benzothiazole mercapto compounds, etc. Or, it is common to include all anti-capri agents. In addition, if necessary, preservatives such as hydroquinolamine/sulfite, organic solvents such as triethanolamine and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, and dyes Forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as /-phenyl-3-pyrazolidone, tackifying agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonic acids. Various chelating agents such as nocarboxylic acids, antioxidants described in West German Patent Application (OLS) No. 2,2,230, etc. may be added to the color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, /-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known black and white developers such as amine phenols such as methyl-p-aminophenol can be used alone or in combination.

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 that can be used include compounds of polyvalent metals such as iron (■), cobalt (III), chromium (IV), and copper (It), peracids, quinones, and nitrone compounds. Typical bleaching agents include ferricyanide; dichromate: iron (II
[) or copal) (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Complex salts of aminopolycarminic acids such as nitrilotriacetic acid, 3-diaminorcozoropanoltetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid; persulfates;
Manganate; nitrosophenol, etc. can be used. Of these, iron(II) ethylenediaminetetraacetate
I) salts, diethylenetriaminepentaacetic acid iron (1) salts and persulfates are preferred from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron(III) complexes are particularly useful both in stand-alone bleach solutions and 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. Patent No. 3. ♂rij, l'j No. 1, West German Patent No. 1,290.11J, 2. (:lr7ri1r, Tokukaisho, f3-J, 27J6, same!3-7713
/ issue, same 37g lt issue, same! ! -1j732, same 13
-726.23, same J3-2! t30, 33-1
1Jj/No., f3-1041.232, J3-
72 Hongu No. 217, No. 13-726.23, No. 13-
No. 726.23, Research Disclosure &/7
Compounds having a mercapto group or a disulfide group as described in No. 2 (July 1973), etc.;
Thiazolidi/derivatives such as those described in '70/22; JP Sho I/-s=trtog, JP Sho J, 2-.
2013! Same issue! ! -3.27.3J-, U.S. Patent No. 3,7OA, j+! Thiourea derivatives described in /; West German Patent No. 1, /, 27, 7/! No., Tokukai ShojJ'
Iodides described in -/1233; polyethylene oxides described in West German Patent No. 91t, Koil O, 2.74'J', +jo; Japanese Patent Publication Akihiro J-1? Polyamine compounds described in JA No.; and other Jikai Sho Gutag λg No. 37;
Getter JFt Google issue, same! 3-Tag No. 727, same j4
t-J,, 1'7.27, same J,! --Otsu! Compounds described in No. 03 and No. 3-110, as well as 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. ♂ri 3. ♂! ? issue,
West German patent No. 1゜Kota0. lf/No. 2, Tokukai Akira! 3-2!
Compounds described in No. t30 are preferred. Furthermore, U.S. Patent No. V3! The compounds described in No.-2♂3 are also preferred. These bleach accelerators may be added to the photosensitive material. Color photosensitive material for photography 1! +These bleach accelerators are particularly effective when total bleach-fixing.

Examples of the fixing agent include thiosulfate, thiocyanate, thiourea thioether compounds, and a large amount of iodide, but thiosulfate is commonly used. As a preservative for the bleach-fixing solution or the fixing solution, sulfite, bisulfite, or a cal+1=bimyelite adduct is preferable.

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 sedimentation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, as well as disinfectants and preventive agents that prevent the growth of various bacteria, algae, and mold. A pasting agent, a metal salt substituted for a magnesium salt or an aluminum salt or bismuth salt, a surfactant for preventing drying load and unevenness, and various hardening agents can be added as necessary. Or Photographic Science & Engineering/Geneering magazine by West (L, E, We
st, Phot, Sci.

Eng.), Volume 1, 34t41-3jr2.
The compounds described in 2.2 and others may be added. The addition of chelating agents and anti-piping agents is particularly effective.

What is the washing process? It is common to save water by using countercurrent flushing in tanks larger than those for seeds. Furthermore, instead of the water washing process,
-, a multi-stage countercurrent stabilization treatment process as described in No. 1'j&J may be carried out. In the case of this process, 1~? A tank countercurrent column is required. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, various buffering agents (e.g., borates, metaborates, borax, phosphates, carbonates, Ihikari hydroxide, sodium hydroxide, monoammonium hydroxide, etc.) to adjust the membrane pH (e.g., pH 3~) Water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. are all used in combination) and aldehydes such as formalin are examples. others,
If necessary, use chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic powder, aminopolyphosphonic acid, phosphonocal/acid, etc.), disinfectants (benziisothiazolinone, isothiazolone, Hiro-thiazoline benzene, etc.) Various additives such as imidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, hardeners, etc. may be used, and two types of the same or different target compounds may be used. The above may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium chloride, ammonium sulfite, and ammonium thiosulfate as a membrane [)H regulator after treatment.

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 70 minutes.
Preferably it is JO seconds to j minutes.

The silver rodanide color photosensitive 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, U.S. Pat. No. 3,341.2. Indoaniline compounds described in J-Li No. 7, Ibid. No. 3, 3-1372, Research Disclosure/4'J' j O and Ibid./! 7 rough base type compounds described in /J No. 3
Tha! Aldol compound described in No. V, US Pat. No. 3,7
/ri, metal salt complex described in 4tri No. 2, JP-A-Sho, +3-/
Including the urethane compounds described in No. 3.1622, JP-A-Sho, rl, -A, 23! No., 3t-/l/, 3
No. 3, same! O-j5', lj,! No. 3-t7g! Same issue! 6-♂373 Hiro issue, same j Otsu-g373 O issue,
The same J Togo No. 3736, the same IT-Zari No. 73j, the same! Bu-
r no? No. 37, No. 74-3411730, No. J[-1
0t, 24t No. 1, same! A-107.2jt No., same, +
7-#7! No. 37 and the same! Examples include various salt-type precursors described in No. 7-♂3J63 and the like.

The silver halide color light-sensitive material of the present invention may contain various /-phenyl-
3-pyrazolidones may be incorporated. A typical compound is JP-A-36-/sI7.339, J7-/4t≠
34L7, same j7-. 2///≠7, same J♂-30
No. 332, same J-1! '-30!3 No. J'g-3
No. 0333, same ll-6033! , same ll-6033!
No. and same! It is described in ♂-//#'7.3g issue etc.

Various processing solutions in the present invention are used at 10°C--5'o'C. 33°C or 3v 0. C is the standard temperature, but it is possible to increase the temperature to a higher temperature to accelerate the processing and shorten the processing time, or conversely to a lower temperature to improve image quality and stability of the processing solution. Furthermore, in order to save silver on photosensitive materials, treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2,2.2A, 770 or U.S. Pat. It's okay.

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.

Furthermore, during continuous processing, a constant finish can be obtained by using replenishers for each processing solution to completely prevent fluctuations in the solution composition. The replenishment amount can be lowered by half or half of the standard replenishment amount to reduce costs.

When the light-sensitive material of the present invention is of color - or 5-color, it is very general that it is a color photographic material for single-color photography, and it can be subjected to a bleaching and layering treatment if necessary.

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

Example-1 (Cleavage of silver halide emulsion) 32g of lime-treated gelatin was added to 7000mg of distilled water, and after bathing at ≠00C, the temperature was raised to a total of 52''C by adding 3.3g of sodium chloride. To this solution M, N
'-Dimethylimidazolidine-corchion (7% aqueous solution) was added for 3.2 hours. A t7 solution prepared by dissolving 32.0i of silver nitrate in 200ml of distilled water and 200ml of distilled water and 200ml of sulfur chloride.
The solution dissolved in m1 and the total,! The mixture was added to the above solution and mixed for 1 minute while maintaining the temperature at 28C. Furthermore, silver nitrate/, 2
g, Of! Add and mix the solution dissolved in total distilled water and the solution dissolved in 4 t + og of sodium chloride, potassium hexachloroiridate (IV) 0 2 l to 0 ml total distilled water over 20 minutes while maintaining the temperature at 29C. did. After being kept at 2°C in the evening, the temperature was lowered to 0°C, followed by desalting and washing with water.

Further, lime-treated gelatin was added to obtain emulsion (A)k.

The resulting emulsion contained cubic silver chloride grains with an average grain size of 00 μ and a coefficient of variation of grain size distribution of o and og.

In emulsion (A,), a mixed solution of total sodium chloride and potassium bromide (the total number of moles is the same, and the molar ratio is g:
2) to obtain a silver chlorobromide emulsion (B) containing silver bromide of λ morti. The addition time of the reaction solution was adjusted so that the average grain size of the silver halide grains contained in the emulsion was made equal to that of the total emulsion (A). The obtained particles were cubic and had a particle size variation coefficient of 0.01.

In emulsion (A), by changing the sodium chloride aqueous solution added together with the silver nitrate aqueous solution to a mixed solution of sodium chloride and potassium bromide (the total number of moles was the same and the molar ratio was set to l:l), 10 A silver chlorobromide emulsion (C) containing silver bromide was obtained. The addition time of the reaction solution was adjusted so that the average grain size of the silver rodanide grains contained in the emulsion was equal to that of emulsion (A). The obtained particles were cubic, and the coefficient of variation in particle size was 0.07.

pL (and pAg) of the three types of emulsions thus obtained
After adjusting the amount of triethylthiourea, chemical sensitization was carried out optimally by adding triethylthiourea to (A-/), (B-/) and (C
-/) emulsion was obtained.

Apart from this, there is also a fine-grain silver bromide emulsion with an average mesh size of 0.0 μm <ai<per mole of silver bromide! , Ta x 70
"Mole of iridium chloride (1v) containing potassium acid)) was prepared by KL', l.

2 mol% as silver halide based on emulsion (A, , )
After adding an amount of emulsion (a-/) corresponding to , triethylthiourea was added to prepare an optimally chemically sensitized emulsion, designated as (A-, 2).

These various types of silver halide emulsions contain the following compounds as stabilizers at a rate of 5.0x per mole of silver halide.
/θ molar classification.

Stabilizer (1-/) One type of silver halide emulsion obtained was examined for halogen composition and its distribution by X-ray diffraction method.

As a result, emulsion (A-/) contained 100% silver chloride, emulsion (B-/) contained 100% silver chloride (silver bromide λ), and
Milk MIJ (C-/) exhibited a single diffraction flake of 0% silver chloride (70% silver bromide). On the other hand, emulsion (A-,
Regarding 2), in addition to the main peak of silver chloride lOochi, there is a center rich in silver chloride 70% (silver bromide 30%), and silver chloride 60% (
I was able to detect a broad sub-peak with a tail around 1, which was around 0.

(Dispersion of homogeneous fine particles of the compound of the present invention) The delivered compound of the present invention having the composition shown below was kneaded and ground into fine particles (having an average diameter of 0.7 μm or less) using a sand mill. Further, citric acid θ, ly was dispersed in a 10% lime-treated gelatin water bath solution and removed using a gold dust glass filter. Using hot water, the compound of Honshusu adsorbed on the sand of the glass filter was also washed off to obtain 1007d of gelatin aqueous solution. All of this is used as a solid fine particle dispersion of the compound of the present invention.

Dispersion A Compound of the present invention (I-λ)...i,,zg(I
-1) ... /, 2g Surfactant (Cpd-10) 5 ml aqueous solution ... 5 ml Dispersion B Compound of the present invention (1-t) ... /, 2
fl(1-,27) ... /, , 29 surfactant (Cpd-70) 5 aqueous solution ..., 5- ml
Dispersion C Compound of the present invention (1-, Ri...'-, 2M
Surfactant (Cpd-//) 5 Aqueous solution...! (Preparation of color photosensitive material) Next, an emulsified dispersion of couplers, etc. was prepared, combined with each halogenated pot emulsion, and coated on a paper support laminated on both sides with polyethylene to produce a multilayer color with the layer structure shown below. Photosensitive material gold was created.

(II# Configuration) The complete composition of each layer is shown below. The numbers represent the coating amount (97 m2; ml/m > e for the solvent. The silver halide emulsion represents the coating amount in terms of silver.

Support material λ - polyethylene laminate paper [white pigment (T i U 2
) and all blue dyes (ulmarine blue)] Gelatin 0 + g.

3 Dye (solid fine particle dispersion) Double layer (yellow color) Silver halide emulsion (Table 1) Spectral sensitizing dye (Table 1) Yellow coupler (Y-1) Color image stabilizer (Cpd-7) Solvent (So1■6) Gelatin 3 (color mixing power ratio) Gelatin filter dye (Dye-4) ・Color mixing prevention agent (Cpd-4) Solvent (SOIV2> (So+v5) Hayatansatsu” Esha Ekumitsu Negative l [Halogenated Silver emulsion (Table 1) Spectral sensitizing dye (Table 1) Supersensitizer (Table 1) Magenta coupler (M-1) Magenta coupler (M-2) (Table 1) 0, 30 Color image Stabilizer (Cpd-1) (Cpd-8) (Cpd-9) Solvent (Solvl) (SOIV2) 0, 12 0, 13 0, 09 Gelatin No. 5 (ultraviolet light n) Gelatin filter dye (Dye-5) Ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-4) Solvent (Solv3) Sixth (cyan color) Silver halide emulsion (Table 1) Spectral sensitizing dye (Table 1) Supersensitization Agent (Table 1) Cyan coupler (C-1) Color image stabilizer (Cpd-5) (Cpd-6) (Cpd-7) Solvent (Solv4) Gelatin No. 7 (Caustic radiation exposure N) Gelatin ultraviolet light Absorbent (UV-1) Color mixing inhibitor (Cpd-4) Solvent (Solv3) Acrylic modified copolymer of No. 811 urine 11 and gelatin polyvinyl alcohol (denaturation degree 17%) - Liquid paraffin yellow coupler (Y-1) ) 1,33 Cyan coupler (C-1) 0,17 0,03 As a gelatin hardening agent for each layer, 1-oxy3,5-dichloro-3-triazine sodium salt was used in an amount of 14.O<2> per tg of gelatin.

2 R=cZH5, CaHq and 2 death! 4:4 mixture (weight ratio) Magenta coupler (M Magenta coupler (M Color image stabilizer (Cpd Color image stabilizer (Cpd 2:4:4 mixture (weight ratio) of Color image stabilizer (Cpd-6) Color image stabilizer (Cpd fcH, -〇　H+.

C0NHC4Hq(t) Color image stabilizer (Cpd Color mixing prevention agent (Cpd Color image stabilizer (Cpd Surfactant (Cpd (Cpd-11) Supersensitizer (Cpd ? capacity Medium (Solv 3) COOCa H+t (CHHz)s COOCgH1? ? capacity Solv-4 (Cpd CH.

CH=CH2 ? capacity Solv melt Solv-5 melt Solv-2 Ultraviolet absorber (UV-1) yes 3° per mole of silver halide 5’X　10-’molt attached added. and Cpd-12 at 2° 6X10-'mol/ Ag was used together.

1) yes t yes 1° per mole of silver halide 7　X　10-’moj! and Cpd 12 to 2° 6 x 10-'mol/Ag p d 13 to 1x10 Used in combination with 3 mol/Ag per mole of silver halide 3,2　X　1. O-5moβ 2-7 X 10-Smoff Ta.

(Dye: 10 cm per m' of coating film (for filters and irradiation prevention) (Dye SC2: 5 cm per coating film) (for filters and irradiation prevention) The above samples were exposed to laser light. Sensitizing dye For samples using Dye-/, Dye-1, and Dye-3f, a laser exposure device indicated by exposure device-/ was used.

The exposure apparatus used in the examples is shown below.

(Exposure device-/) Semiconductor laser AlGa1. nP (oscillation wavelength, approximately 470 nm), semiconductor laser GaAlAs
('d vibration wavelength, approximately 7 j On m), GaA
IA, s (oscillation wavelength, approximately ♂3 o nm)'e was used. An apparatus A was assembled in which the laser beams were sequentially scanned and fogged onto color photographic paper using rotating polyhedrons that moved in a direction perpendicular to the scanning direction. The exposure amount was electrically controlled by the exposure time of the semiconductor laser. (The exposure apparatus used in the present invention is disclosed in the patent application filed in 1983-22 filed by the present applicant).
6!52 Specification 1) Using the above-mentioned exposure apparatus, semiconductor laser sources with a luminous flux wavelength of about 70 nm, about 76 On, m, and about 130 nm were used, respectively, so that the exposed body had a VC of about 50 μm. The output was adjusted and exposed. Bottom = tv It was developed through the processing steps shown below.

On the other hand, a CT F measurement chart was closely attached to each sample to provide a reference point for measuring resolution. The lighting used was a xenon light source with a bandpass filter IF-8 manufactured by Nippon Vacuum Optics.
Ultra-thick transmission wavelength of the mold, &70nm, 7nm and 1
The light was passed through each filter of 30 nm, and the amount of light was adjusted using a HeD filter. The heart rate was approximately 70 seconds. It was developed through the processing steps shown below. The obtained yellow magenta and cyan colored images were subjected to magnetic field measurement using a micro reflection densitometer with an aperture of .mu.m.times.4 to .theta..mu.m to obtain a CTF curve.

The sharpness of the edges of line drawings obtained by exposure to semiconductor laser light, and the CTF (number of lines at 0.5 straight lines/
The values of mm are shown in Table 1.

The treatment steps used and the composition of each treatment liquid are shown below.

Processing process Temperature Time Color actual 1
S/! I 350C≠j seconds Hohaku set 30
~3pm 0C Hiro! Rinse for seconds■ 30~3!0C Rinse■30~3!0C Rinse■30~3!0C Rinse■30~3!0C Dry 70~I0 0C (Rinse■→
The three-tank countercurrent flow system and the composition of each treatment solution are as follows.

Color developer water Ethylenediamine-to, N, IN'-tetramethylphosphonic acid triethylenediamine (/, 4t diasabinchloro [λ,, 2..2) octane) Sodium potassium carbonate ~-to-ethyl- (β-methane Sulfonamidoethyl)-3-methyl-Hiro-aminoaniline sulfate,! θ seconds + 20 seconds, 20 seconds to 20 seconds to paper cutting. ) r θ OmL /, j9 Yu, Oy /, Hirogs, og N, N-diethylhydrokineluamine fluorescent brightener (UVITEX CK, manufactured by Chipagaigi) Add water to pH (230C) Bleach-fix solution water thio Ammonium sulfate (70%) Sodium sulfite Ethylenediaminetetraacetate Iron (III) Ammonium Ethylenediamine Tetramethane Trilam Ammonium Bromide Glacial acetic acid water? In addition, pH (J 5°C) Rinse liquid ion-exchanged water (Calunium, Magnesium is each Hiroshi, 2g, oH 1000mlV 10.10g 00ml 100 ♂g Tatay 3g ≠Og ♂g 7000g!, Tough 7 31) rim and below) ○Sharp △Normal × Blurred By the present invention, it is possible to significantly improve the resolving power and sharpness of the edge. In particular, the samples - Hiro and Trial Otsu are yellow,
Shows excellent edge sharpness across magenta and cyan images. Sample 2 had a slightly lower sensitivity in the second layer (cyan color development), but an excellent image was obtained with particularly high saturation of yellow, magenta, and cyan images (good color separation).

In addition, none of the 6 bright samples of the present invention had any color staining due to the residual color VC caused by the compound of the present invention, and a whiteness equivalent to that of Sample 1 of the comparative example was obtained.

Example 2 Gelatin sog was bath-dissolved in water, 30 days of aqueous solution of sodium dodecylbenzenesulfonate was added as a surfactant, and /-hydroxy-3,!-dichlorotriazine sodium was added as a hardening agent. A 1-liter aqueous solution of salt was added to the mixture, and a solid 9-particle dispersion of the compound of the present invention shown below was prepared.That is, the crystals of the compound of the present invention were kneaded, and fine particles (the Average diameter is 0.75μm
(below). It was further dispersed in 2ml of 1Oqb lime-treated gelatin aqueous solution dissolved in citric acid (O,H)2, and the used sand was removed using a glass filter. Compounds adsorbed on the sand on the glass filter were also washed away using hot water to obtain a 7% gelatin aqueous solution of 100%.

Dispersion A Compound of the present invention (■-g)...0.7g Surfactant (Cpd-to of Example 1) 5% aqueous solution
... Compound (1-, ?7) of snr dispersion sales... -o, ? 9 surfactant (Cpd-10 of Example 1)! aqueous solution
... 5m1-C lower I for sword comparison
The same τ>, t as the above i-♂, l-, 27 solution of P-dye a
7 JL] and the total amount was adjusted to 71. This gelatin-containing water bath solution was applied onto a polyethylene-coated paper support so that the dry film thickness was ≠ μm. -Silver chloroiodobromide chemically sensitized by a sulfur compound (
The emulsion contains 30 mol% of odor, 0.1 mol% of iodine, and the average diameter of silver halide is 0.3θ microns).
E, '4t% mep no) and add bath liquid jOrdf,
t of Cpd-/2 in Example 1.

O weight ratio methanol solution 3ome, Cp d of Example 1
-/ 3t! J) 0, tieht% melting, 2Crrd
and lower ieCp d −/≠0. tM amount % bath gauze. m
l and total 7J[]e, = 75- ranidodenlebenzene sulfonic acid soda,.

Add 301 nl of weight related aqueous solution, /-hydroxy-3°! -Dichlorotriazine sodium salt/, 0% by weight The entire aqueous solution was added, stirred, and coated on the gelatin-coated surface of the support. Furthermore, a water bath coat containing gelatin and sodium dodecylbenzenesulfonate was applied as a coating layer on top of the coating.

The film K (A) 7 A On thus produced
Light emitting diode (B) 71r3nm semiconductor laser is used to emit hesitating light and developed by Fuji Photo Film.
l)-135 to automatically operate the current 1st area machine FG-do o [
(A (manufactured by Fuji Photo Film)) was processed at 310C for 20 seconds.

Image quality was evaluated on a J scale from 〆 (extremely poor image quality with many fringes) to evening (sharp image with no fringes). The evaluation of residual color is / (very much residual color) to j
(no residual color at all). In the case of evaluating fringe and residual color, visual observation is more sensitive than measurement using equipment, and visual evaluation is also performed in actual use of photosensitive materials.

The results are shown in Table 3.

Dye-7 Comparative dye a is the following dye of British Patent No. 31A, No. 171.

Cpd- is CH2-CH=CI(2) As is clear from Table 3, when the dispersion of the present invention is used, images with good image quality and less residual color can be obtained.

Example 3 A fine particle dispersion of a compound of the invention prepared in the same manner as described in the previous example was applied as a dye layer of the lower HQ content to both sides of a primed & 775 μm blue-dyed polyethylene terephthalate film. The second undercoat was 1 so.

Furthermore, an emulsion layer and a surface protective layer having the following contents were coated on both sides to prepare photographic materials 3-/-3-B.

(Dye layer content - per side) O gelatin 0, / 29/m2
Q Microcrystalline dispersion of the compound of the present invention or comparative compound (emulsion layer contents) Preparation of emulsion layer coating solution Kalita bromide 9, potassium iodide, osg, gelatin 309, thioether HO (CI(2)) 28(C)i2 )28(CH2
) 201 (glue % aqueous solution co, 750C with the addition of glue CC
An aqueous solution of 1.33 g of silver nitrate and an aqueous solution containing 0.7269 g of Kalita bromide and TAG S1 potassium iodide were added to the bath solution maintained at a temperature of ≠5 seconds with stirring. Next, potassium bromide 2. After the addition in the evening, an aqueous solution containing nitric acid @ 3 J pi was added over a period of 7 minutes and 30 seconds so that the flow rate at the end of the addition was twice that at the beginning of the addition. Subsequently, an aqueous solution of silver nitrate/3.3119 and an aqueous solution of potassium bromide,! It was added over two evenings using a controlled Damel jet method while maintaining the position at pAgf, /. The flow rate at this time was accelerated so that the flow rate at the end of addition was r times the flow rate at the start of addition. After the addition is complete! 1N thione was added over 12 cc of the potassium anate bath solution listed in Table 1, and further added over θcc of 1% potassium iodide bath solution.

After this, the temperature was lowered to 0C for 3 nights, soluble salts were removed by the sedimentation method, and then the temperature was raised to ao 0C and gelatin ttr
g and phenol 2L trimethylolpro/ξn7.
Add 5g and adjust the pH to 4 with sodium chloride and potassium bromide.
Hiro 0. pkgr, adjusted to Hiroyu.

After raising the temperature to S&OC, 620 μ of a sensitizing dye having the following structure was added. After io minutes thiosulfate (h')
Ram 5 hydrate 1.6m9. Potassium thiocyanate/131
nfi, chloroauric acid 3.1. 9f m was added, and in the evening it was rapidly cooled and solidified. In the obtained emulsion, 23% of the total projected area of all grains consists of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more is 0.13 μm, with a standard deviation of l. ♂, bu-, the average thickness is 0. /l, 18m, and the aspect ratio was /1.

r 0 The following chemicals were added to this emulsion per mole of silver halide to prepare a coating solution.

・Co,6-bis(hydroxyamino)-goodiethylamino-/, 3. Tatriazine Tahiro, 5m? Fist sodium polyacrylate (average molecular weight゛≠, 171') 2-77i・
Ethyl acrylate/acrylic alcohol/methacrylic acid = Ri! /, 2/3 composition ratio gold plasticizer, 2≠, 19-4/ ・Potassium bromide 77■ Coating fM of emulsion layer is per one side, ・Amount of silver coated /, 7 g 7m2
・Coated gelatin amount 7,7 g 7m
2. Polyacrylamide (average molecular information, j million) 0, 'I 7 i
/ m2.

(Contents of surface protective layer) The coating amount of the surface protective layer was as follows per one side.

No. gelatin /, 9/m2, polyacrylamide (half-uniform molecular weight, 1,000 yen) 0, . 239/m
2. Matting agent (average particle size 3.5 μm) 0.0!97 m2 Polymethyl methacrylate/methacrylic acid = Ri, l cofiltration aggregate -C16H-330 (CH2C1-120) 10 H.
Qlt(1□So 2N(CH2CH20)1 s H
3H7, 20mli/m ri~/m' ・Hiro-Hydroxy-Otsu-methyl-/, 3.3a, 7-chitrazaindene, 2/, 7■/m2 Hardener u, i,, z-bis(sulfonylacetamide) ) Ethane was applied at a rate of 57 μm/rn per coat.

(Photography performance evaluation 1'III) For the exposure of photographic materials 3-/-3-B, G of Fuji Photo Film Co., Ltd.'s GRENEX series was used as a screen IJ.
−≠ Screen was used. According to the usual method, Q-! Photographic material for one fleece! -g', and exposed to X-rays through a water fan dome of 10 cm'.

For processing after exposure, use Fuji Photo Film's FtD in the developer.
-1111 at 3r0c, using Fuji F manufactured by the same company as a fixer, and an automatic processor processing using FPM-qooo manufactured by the same company.

The sensitivity was expressed as a relative sensitivity of photographic material 3-/f100.

(Measurement of Sharpness (MTF)) MTFk was measured using the combination of the G-Hiro screen and automatic processor processing. Measured with an aperture of 30μm x jOOμm, and the spatial frequency is l.

Using an MTF value of Q cycles/mm, the optical density is /,0
Evaluation was made on the 0 part.

(Evaluation of residual color) Further, the unexposed film of the photographic material described above was subjected to the above-mentioned processing, and the level of residual color was subjected to a full sensory evaluation.

A... is a state where you can hardly tell that there is any residual color (...
・I notice that there is some residual color, but in practice it doesn't bother me at all E... There is clearly residual color, and the residual color is practical -
Hiroshi: It was a state of concern, and B and D were intermediate states.

The results of the above evaluation are shown in Table 1 along with the sample contents.

From Table ψ, it can be seen that the photographic materials 3-7 to 3-7 of the present invention are excellent in relative sensitivity, sharpness (M, TF), and persistence of residual color.

Example 4 After corona discharge treatment on paper supports laminated on both sides with polyethylene, paper support samples A, B and C were coated with gelatin subbing layers or dispersions of the compounds of the invention below.

(Dispersion method of the compound of the present invention) The following crystals of the compound of the present invention were kneaded and made into fine particles using a sand mill. Further, V was dispersed in 23rd aqueous solution of 20% lime-treated gelatin dissolved in citric acid O, Zy2, the used sand was removed using a glass filter, and the uninvented compound 1-/・ was added to the sand on the glass filter. ...00r
yCompound 1-23 of the present invention...o, tH
and 7 Winter comparison compounds 1 and 1 dissolved and became uniform when dispersed.

Comparative Compound/(Surfactant) 5. The cured compound was removed and 70ON of 7% gelatin solution was added. (The average particle diameter of the fine particles was 0./μm.) Paper support A Undercoat layer gelatin ...0, I
, j9/m2 Paper support B Harenyon prevention layer gelatin...0,1.
g/m2 Compound of the present invention 1-/...
2 mg/m2 Compound of the present invention I-, 23...
... aomg7m2 paper support C halayon prevention layer gelatin ...0, l,
9/m2 Compound of the present invention 1-/...
・・110 m9 / rn2 Uninvented compound I-j
3...6.../m2 Multilayer color photographic paper samples G/ to P-G having the layer structure shown below were obtained on paper support samples A, B, and C.

The coating solution was prepared as follows.

1g - Preparation of 1st layer coating solution Yellow coupler (ExY) 1g and color image stabilizer (Cpd-/) Hiro, ≠g and (Cpd-7)/, 1
f) L, 27, J CQ and solvent (
Add 1 g of each layer of SOIV-3) and (Solv-6), dissolve in a bath, and convert this bath solution into a 70% gelatin aqueous solution containing to% sodium dodecylbenzenesulfonate ICCk/rec.
cVC was emulsified and dispersed. On the other hand, bulk silver bromide emulsion (10, θ morti, cubic, average grain size θ, rjμ, coefficient of variation o
, or, and silver bromide io, o mole strip, cubic, average grain size 0.62 μ, coefficient of variation 0.07.
．． Mixed at a ratio of 3 parts (A, g molar ratio)) 1 yellow sensitized with sulfur, the following blue-sensitive sensitizing dye was added per 1 mole of silver.
f, 0x70 moles were prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

The coating liquids for the second to seventh layer phases were also prepared in the same manner as the coating liquid for the first layer. l-oxy-3,turnchloro-8-triazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer (CH2)4 (Ct(2)48038-N(C2t(s)3 (halogen per 11 mole, 0x10' mole) SC1
3H-N (C2Hsh (4t per mole of silver halide, O x 70' mol) and so'Hso3 i-i.N(C2H5)3 (7.0 x 70 mol per mol of silver halide) c2t- i
51 (,:5H□1 (Target 0, ×10 mol per mol of silver halide) For the red-sensitive emulsion layer, the following compound was added per mol of silver halide at 2.6
×70−3 mol was added.

In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, /-(j-methylureidophenyl)-termercaptotetrazole per mole of halogenated button ≠
, o×io' mole, 3゜0×10 mole, /,
O×10 mol, and no methyl-j=t-octylhydroquinone, respectively l×10” mole, 2×10, λ×io per mole of silver halide.
``Added.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, Hiroshi-hydroxy-6-methyl-i and 3*3a + 7-titrasaindene were added per mole of silver halide, respectively.
2×10 ”mol/l×10 ”mol were added.

One paper support sample A had the following comparative dyes added to its Emulsion H.

ta/-1 tako and...2 gu/m2 (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/d). The silver halide emulsion represents the coated amount in terms of silver.

Four kinds of samples A, B, and C were prepared by providing an undercoat layer and an antihalation layer on a polyethylene laminated paper [the first layer of polyethylene contains a white pigment (TiO□) and a bluish dye (ulmarine]). 1 Yu Kosumi 1 and the aforementioned silver chlorobromide emulsion (AgBr: 80 mol%) 0, 26 1, 83 0, 83 0, 19 0, 08 0, 18 0, 18 Gelatin yellow coupler (ExY) Color image stability Agent (Cp, d-1) 〃 (Cpd-7) Solvent (Solv-3) 〃(Solv-6χ Second layer (color mixing prevention N) Gelatin 0,99 Ri 3 Color mixing prevention agent (Cpd-6) 0.08 solvent(
Solv-1) 0.16〃 (Sol
v-4) 0. 08 Ura EF”
(4 Gen 11 and silver chlorobromide emulsion (AgBr 90 mol%, cubic, average grain size 0.47μ, coefficient of variation 0.12), AgB
r 90 mol%, cubic, average particle size 0.36μ
, and those with a variation coefficient of 0.09 are mixed at a ratio of 1:1 (Ag molar ratio)) 0.16 Gelatin 1. 79 Magenta coupler (ExM) 0.32 Color image stabilizer Cpd-3) 0. 20 (Cpd
-8) 0.03 (Cp4-4)
0.01 (Cpd-9)
0.04 Solvent (Solv-2) 0.
65 4th U outside line) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (Cp
d-5) 0.05 solvent (Solv-5)
0.24th Qil'' (, blasphemous and chlorbrominated iff (AgBr70 mol%, cubic, average particle size 0.49μ, coefficient of variation 0.08) and AgBr
70 mol%, cubic, average particle size 0.34 μ, coefficient of variation 0.10, mixed at a ratio of 1=2 (Ag molar ratio) 0.23 1.34 0.30 0.17 0.40 0.20 Gelatin cyan coupler (BxC) Color image stabilizer (Cpd-6) // (Cpd 7) Solvent (Solv-5) SixP (purple line absorption) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5)? Container (3o1v-5) 0,53 0,16 0,02 0,08 Gelatin 1.33 (Cpdl) Color image stabilizer Acrylic 0° modified copolymer of polyvinyl alcohol (degree of modification 17%) Liquid paraffin 0゜ (Cpd Color image stabilizer (Cpd Color image stabilizer (Cpd Color mixture prevention agent (Cpci-7) Color image stabilizer ○ TOTO CON HC-Hq (t) Average molecular weight (Cpd Color image stabilizer (Cpd Color image stabilizer Agent (Cpd-9) 2:4:4 mixture of color image stabilizer (weight ratio) 10(] (UV Ultraviolet absorber (Solv 2:1 mixture of solvent H (volume ratio)) (Solv Solvent (3o1v 4) ? 4.:2:4 mixture (weight ratio) of medium (SOIV Solvent (Solv Solvent COOCs HI3 (CH2)s COOCa HI7 (Solv 6) ?Vehicle (ExC) Uncoupler (Ex x Y) Yellow coupler Obtained sample About Hiro-/or Gu Hiro, a sensitometer (manufactured by Fuji Photo Film ■).

FW day type, of light source (ExM) Magenta coupler color temperature 3 ．． 200 'K) to blue, green and red valley Filter wk and sensitome to stair dew for no gave light.

On the other hand, Resolution ( CTF) measurement Perform the exposure of after that, Perform the following development processing. Ta.

The concentration of the obtained sample was measured and the results are shown in Table 5 (1) Fruit (!l-gotta).

-70≠- (Processing process) Treatment process temperature Color development 37°C Bleach fixing 33’ (: Water washing, 2g ~ 34t’C Dry journey 7o-tro 0c (processing liquid) Color development number water Diethylenetriamine 5tr+m: Nitrilo 3l! ! i'I acid l-Hydroxyethythelene-l.

Phosphonic acid (to% solution) Benzyl alcohol diethylene glycol Sodium sulfate Potassium bromide Potassium carbonate - Ethyl N- (β-methanesulfonamidoethyl) - 3:19] 3 minutes 30 seconds 7 minutes 30 seconds 3 minutes 1 minute and 0 0 m, e i, og co, Og /, Oml! 5ml 0ml!, Oy /, Og 0 g -methyl-hiro-aminoaniline sulfate g, rig hydroquine luamine sulfate 3. Agent (WHI
Add TEX water / 000 punishment pH (
,2ta 1JC) to,,
2r bleaching layer liquid water 110
0ml ammonium thioborate (70%) iro
mi sodium nitrous acid /11/
Ethyleneaminetetraoxalate iron (river) ammonium! ! g Disodium ethylenediaminetetraoxate Add 5g water and make 7000ml 1p l-1, (
2J-°C) 6.70 Rinse water Water treated with ion exchange as shown belowTap water Deionized with total ion exchange fat to remove calcium and magnesium respectively. ppm or less,
Additionally, sodium incyanurate dichloride, 20 ppm'
It was used after adding e. The pH of this water was Otsu.

When the compound according to the invention is used in an antihalation layer,
There is relatively little decrease in sensitivity and no noticeable residual color. By using such an amount, the resolution can be significantly improved.

Support sample B or Ci was used, and high silver chloride emulsion IIi was applied thereon.
Color photographic paper (EP No. 1,
273μ22, 273≠30 and patent application Sho t3-7
Similar results of 7″i can be obtained for the multilayer structure described in the specification of No. 16/2013.

Example 5 The blue-sensitive emulsion used in Example 4 was added to a silver chlorobromide emulsion with a silver bromide content of 0.6 mol (cubic shape, average grain size O3rμ coefficient of variation 0.0), and the edge-sensitive emulsion was added to the odor-sensitive emulsion. Silver oxide content 1.2
Molar silver chlorobromide emulsion (cubic, average grain size 0.7
The red-sensitive emulsion layer has a λμ variation coefficient of 0.07) and a silver bromide content of 1. Example 4
In the same manner as above, a sample tar/karatar μ corresponding to the sample Gu/kara Hiro-Hiro was created.

The blue-, green-, and red-sensitive emulsions contain the following spectral sensitizing dye and cpct-10, and silver bromide exists in a part of the grains forming a localized phase.

Blue-sensitive emulsion layer (per mole of halogenated H),
Halogen 7 (a, oxio' mol per 11 mol) and S (J3H- to (C2t(5) 3 (tariff, 0x10-5 mol per mol of silver halide)) red-sensitive emulsion layer (each emulsion has a halogen per mole of silveride!×1o
The same test as in Example 4 was conducted using the obtained sensitive material using the following processing solution and processing steps, and samples j-3,! -≠ had higher sensitivity in the red-sensitive layer and the green-sensitive layer than the sample tar λ. In addition, the Dmin of samples 3 and j was as low as that of the turquoise sample, and the resolution was sharper than that of the other samples as shown below.

C3t(11 (Halo'y'Tari 0.2 x 10-4 mol per 1 mol of silver heptide) -///- //2 Processing process Temperature Time Color development
3yo0c Hiroyu Second Bleach Gradual 30~3
6°C Hiroyu seconds stable■ 30-37°Cxo seconds stable■ 3o~37°Cio seconds stable■ 30-37'C, 20 seconds stable■
Dry at 30 to 378C for 30 seconds and 70 gs for 10 seconds (stable ■-■≠tank countercurrent method).The composition of each treatment solution is as follows.

Color developer water Ethylene diamine Shizusaka Triethanolamine Sodium chloride Potassium carbonate He Ethyl he-(β-methanesulfonamidoethyl)-3 Monomethyl-≠-Aminoaniline sulfate! , θgr OO Biao λ , OI g, oy /, 4t9 2 + Oy to, Hediethylhydroxylamine! , t-dihydroxybenzene 1/, 2, Hiroshi-trisulfonic acid fluorescent brightener (G) Add cyanide water and pl (bleach-fix solution water ammonium thiosulfate (70%) sodium sulfite ethylenediaminetetraacetate iron (11 ) Ammonium ethylenediaminetetraacetic acid disodium ice l￥1.Add acid water and add H≠, 2g 0.3g l Q Q 0M 10.10≠00rrd3 ) o, tg formalin-sulfite adduct 0.7 g!-chloro-methyl-hiro-inthiazolin-3-one 0.02 g co-methyl-hiro-inthiazolin-3-one o, oiy Add water, pH around 100θ, Example 6 A sample tO/W, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared on a tri-acid cellulose film support which had been fully undercoated.

(Composition of photosensitive layer) The coating amount is expressed in units of g/m2 of silver for silver halide and colloidal silver, and the amount expressed in units of 97 m2 for Kabra, additives and gelatin, and the amount expressed in units of 97 m2 for sensitizing dyes. The number of moles per mole of silver halide in the same layer is expressed.

//For chemical structural formulas that take the form of salts, we follow the chemical abstract notation.

7th layer (antihalation layer) Black colloidal silver...0. /j gelatin
.../, riUV-/(ultraviolet absorber)...o, o3UV-,2 (ultraviolet absorber)...0.06UV-3<ultraviolet m absorber)
-o, o7 Solv -, 2 (Solution 11 Li)...
o, orExF-/(cyan dye)...0.07Ex
F-,2 (cyan dye) -0,07 2nd layer (low-sensitivity red-sensitive emulsion layer) Agi Hiromorchi Uniform Spherical equivalent diameter o, qμ Number of fluctuations in sphere equivalent diameter 37%, plate-like grains Diameter/thickness ratio 3 .0 Gelatin EXS-/EX, S-,2 EXS-Yellow coated silver td...O...O (sensitizing dye)...t (sensitizing dye)...0 (sensitizing dye) ...6 1//,! ;- ≠ , ♂ , 0x10' , /X10' , Yu×lO4 EXS-7 (sensitizing dye)... Bow,! ×10ExC-/
(Cyan coupler)...0,/7 ExC-,2 (Cyan coupler)...O, OtaExC-3 (Magenta colored cyan coupler...Oo
3I (medium-sensitivity red-sensitivity emulsion island) Silver bromide emulsion (AgI4 molar ratio, core-shell ratio λ; internal height of AgI, equivalent sphere diameter O, tSsμ, coefficient of variation of equivalent sphere diameter, 2j%, plate shaped grains, diameter/thickness ratio 2.0) Coated silver amount: O, S silver iodobromide emulsion (A g I ≠ molar folds, uniform-Agi type, equivalent sphere diameter 0.1.1 μ, equivalent sphere) Coefficient of variation in diameter: 37 cm,
Spherical particles, diameter/thickness ratio 3.0) Coated silver 8it...0
．． / Gelatin.../90EXS-t (sensitizing dye)...5.0×1O-4EX, S-,! (Sensitizing dye) ・・・0.2×IQ 'EXS-(Sensitizing dye) ・・・t,, 2×10 4EXS-7(Sensitizing dye) ・・・1.2×70 ``ExC- /(Cyan coupler)...0.37 ExC--2(Cyan coupler)...0,0/ExC-3<Magenta colored cyan coupler)...0
．． 02 Hiro layer (high-sensitivity red-sensitive emulsion layer) silver bromide emulsion (Agl Otsu Morch, core shell ratio 2:
l internal height Ag1 type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter, 25%, root-like particles, W diameter/boring ratio 1. Coated silver amount...O, Tagelatin...o, 1EXS-/ (
Sensitizing dye)...4. l/1X104EXS-2 (sensitizing dye)...Ol x1O-4EXS-ta (sensitizing dye)...10. G×1O-4EXS-7 (sensitizing dye)
...10. ≠×104ExC-/(Cyan coupler)...0.07 ExC-≠(Cyan coupler)...0.02 Solv-/(Cyan coupler)...0
,07Solv-,2(Solution4j)-0,07S
olv-3() -o-o, :zCpd-7 (antifoggant)...Hiroshi, t×i.

+2,0 @ layer (middle layer) gelatin/...O1UV-≠(ultraviolet absorber j)...0.03vv-r<
Ultraviolet absorber)...o, ottcpct-/(color mixing prevention agent)...0. /Polyethyl acrylate latex 0, O, etc. 5olv-/(Solvent) 61st wheel (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion A-gI+molar average type. Equivalent sphere diameter θ, ≠
μ, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 37%, plate-shaped particles, diameter/thickness ratio//Water cloth silver content...0. I1 Gelatin...O7 HiroExS-3<sensitizing dye)...λ×l0-4EXS-
Hiro (sensitizing dye)...7 x 10'ExS-Y (sensitizing dye).../x/θ-4ExM-ta (magenta coupler)...0, // ExM-7 (yellow) Colored magenta coupler) 0.03ExY-f (DIR
Coupler)...0.07 Solv-/(Solution 1li)...O, θ
Run 5olv-≠(solvent) -0,0/71st ship (medium opening green-sensitive emulsion layer) silver bromide emulsion (Agl ll-molar fold, core shell ratio /:/ surface pan AgI type, sphere equivalent type , equivalent sphere diameter O, Sμ
, coefficient of variation of equivalent sphere diameter, 20%, root-like particle, diameter/thickness ratio, 0) Coated silver amount...0. ．． 27 -7.20- Gelatin...0.6ExS-3 (sensitizing dye)...2 x 10'E x b-≠ (sensitizing dye)...7 x 70'EXS-3 (sensitizing dye) dye)
.../×10 'ExM, -j (magenta coupler) ...06 t 7 ExM-7 (yellow colored magenta coupler)
...0.0μE x Y −f (
DIR coupler) 0.0.2 80]V/(solvent) -o,, 1aSolv-
Hiro (solvent) -0,02 and 1 (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (A g I, 7 mol%, silver 11 ratio 3, g; 2 multilayer structure grains, containing Ag1 11. From the inside, 2 mol, θ mol, 3 mol%, equivalent sphere diameter 0.7μ
, coefficient of variation of equivalent sphere diameter, ! Coating material, plate-like particles, diameter/total ratio 1.6) Coated edge amount...0.7 Gelatin...0. ♂ExS-1I (
Sensitizing dye)...5.2×70 'ExS-ta (sensitizing dye).../×70'ExS-f (sensitizing dye> -o, z×to'ExM-ta (magenta coupler)・0, / ExM-4 (yellow colored magenta coupler)
...0.03ExY-J'(DIR, #
Blur)...0,02 ExC-/(Cyan coupler)...0.0.2 ExC-1(Cyan coupler)...O+ 07 SOIv-/(Solvent) -0,2 5olv-,2
(Solvent) ・ o-otSolv-1'(# agent)
-0,0/cpd-7 (antifogging agent).../×10' 2nd layer (intermediate layer) Gelatin...0.3 cpct-/(color mixing inhibitor)...0.0 gpoly Ethyl acrylate latex...0,/2 Solv-/(solvent) -0,02'MOON<donor of interlayer effect for red-sensitive layer 1-) Silver iodobromide emulsion (A
gIA moltimol ashel ratio 2; l inner cylinder AgI type,
Equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 2μ, plate-like grains, diameter/thickness ratio 2.0) Coated silver circle...0.6r Silver iodobromide emulsion (A, gI + moles, Coefficient of variation of uniform sphere equivalent diameter: 37%, root-like particles, diameter/thickness ratio: 3.0) Coating silver thickness: 0. /Tagelatin °°゛/・0ExS-3 (sensitizing dye) ...6×/θ-4ExM-10 (DIR coupler) ...Q, /ri5olv-/(solution/Jj) -0,20Sol
v-3-0, 0r -/, 23- 1st/layer (yellow filter layer) Yellow colloidal silver...0.06 gelatin
... o, rcpa-2 (yellow dye) ... 0.73 Solv-/ (solvent) -0, /3 cpd-/ (color mixing prevention agent) ... 0.07 Cpd-1 (antifogging agent) ・...0, 002 H-/(hardener) ...0.13 12th) *<
Low-speed blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl Hiroshi, t molar ratio, uniform A, gI
Type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter l height, plate-like grains, diameter/thickness ratio 7, O) Coated silver iij...O8j Silver iodobromide emulsion (AgI 3 mol%, uniform AgI) Mold, equivalent sphere diameter 3.0μ, coefficient of variation of equivalent sphere diameter 30%, plate-shaped particles, diameter/thickness ratio 7.0) For coated iron...0. ．． 2! -7+2≠ Gelatin.../, IEXS-6 (sensitizing dye)...ri x 70 'ExC-/(cyan coupler)...0.01 ExC-4t (cyan coupler)...0,03 ExY-ta (DIR coupler)...0. / HiroExY-//(yellow coupler)...0+dori8o1v-/(solvent) -0,4t2 13th layer (intermediate layer) Gelatin...0.7ExY-/2
(DI R coupler)...0. ．． 20 Solv-/(solvent) -0,311 74th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (A, gI 10 mol%, inner cylinder AgI
Type, equivalent sphere diameter/, θμ, coefficient of variation of equivalent sphere diameter, 2%,
Multiple double root-like particles, diameter/roof ratio! , 0) Amount of coated silver...0.5 Gelatin °0・ExS-4 (sensitizing dye).../×10ExY-ta(1
)IEL coupler)...0.0/ ExY-//(yellow coupler)...0.20 ExC-/(cyan coupler)...0,02 Solv-/(solvent),,,o,i .

1st rr*<1st protective layer) 9-sheet bromide milk tea (AgI 2 mole head, AgI type, equivalent sphere diameter 0.07μ) Coated silver amount...O1/2 Gelatin...o,! 1lUV-≠(
Ultraviolet absorber)...Q, //UV-ta (ultraviolet absorber)...0. /1Solv-j (bath Mll) =0
・02H-/(hardening agent)...θ, /3 uniformity-Cp d-! (Scavenger)...0,70 Polyethyl acrylate latex...OoO UV-/ 16th layer (λth barrier layer) Fine grain silver bromide emulsion (Agl 2 mol ratio, uniform AgI type, equivalent sphere diameter 0.0
7μ) UV-2 C@3-C-CI (3 CH3 Coated silver amount...0.36 Gelatin...0.! Polymethyl methacrylate particle diameter 1. Evening μ...0.2 H-/ (Hardening agent) In addition to the above ingredients, each O1/7 layer contains emulsion stabilizing piece 1cpd3 (0.07i/
m2) Surfactant Cp d -If (o, o311/m
No. 21 was added as a coating aid.

UV-3 H3C-C-CH3 CH3 -7,27 /+2! r- V-3 CN -/2ter= 工U ShikuJ(,1 = = 3 し■ 〇- 杢○=○ ○ ExF-2 (CH2+3SO3- (CH2+3803t( ExS-yoCt-+2 CH2 O3 CH2 +32 03K ExS-A (CI(2)4 (CI(2)4 O3 O3H He C2H5 \ 2H5 ExS S 03 Na S(J3 2H5 He C2H5 2H5 ExS-7 \ ExS-1 2H5 ExC-/ -/3≠- ￥ ) Cpd-B Cpd-μ H-/Cpd-2 (i) CB) 117 (JC(JCH2(i)
Csf-117QC(JCH-8O3Napd-f Cpd-4 Cpd-3 C1(3 cp d-10 CsF17802N(C3H7) CH2COOK-/3
f-1/3! P- (Preparation of sample AO2) Black colloidal silver in the first layer of sample 6θ/ was replaced with a fine particle dispersion of compound 1-, f(0,2E//m2) of the present invention. A dispersion of compound i-7 of the present invention was prepared by the following method.

Water (2/, 7ml) and j% aqueous solution of p-octylphenoxyethyneethaneethanesulfonate sodium 3m
l, s% water bath solution of p-octylphenoquine poly(degree of polymerization 10) ethylene ether O1 and f 700
ml Botmill, compound of the invention 1-i,o
og and zirconium oxide beads (diameter/mm) 500
mlf was added and the contents were dispersed in a vibrating ball mill for a total of 2 hours. The vibrating ball mill used was a BO type manufactured by Chuo Kakoki.

All contents are destroyed/2. A gelatin dispersion of Compound 1 of the present invention was obtained by adding it to an aqueous gelatin solution R9 and passing through beads.

(Preparation of Sample O3) Sample O≦1602 was prepared in the same manner as 1/O Sample 602, except that Compound 1-7 of the present invention was used instead of Compound 1-7 of the present invention.

(Preparation of sample to≠) In sample t02, compound 1-7 (, 0, #/m ) of the present invention and 1-.
Sample 60 except that 2g (Q, 7g7m2) was used at the same time.
It was prepared in the same manner as λ.

(Preparation of Sample 60j) In Sample 60, the following comparative compound B/(Special 1ff'l Akiori No 7.
It was produced in the same manner as samples to, :z except that the compound described in No. 27/4) (0-2 g/Iη) was used.

Comparative Compound 6-/ Samples 107-60 obtained as above! After being exposed to light, it was processed according to the method described in Table 7 (C).

/II-/ Table 7 Treatment method Next, the composition of the treatment liquid will be described.

Color developer (unit 9) Diethylenetriaminepentaacetic acid / -Hydroxyethylidene-17 1-phosphonic acid Sodium sulfite Potassium carbonate Potassium iodide / , 0 3 , 0 ≠ , 0 30.0 / , G / , 5m9 Hydroxylamine Sulfate Hiroshi-[H-ethyl-(β-hydroquinethyl)amine] -2-Methylaniline sulfate was added to pH 10.05 (Unit I ethylenediaminetetraacetic acid). Diiron ammonium dihydrate ethylene diamine tetram acid disodium salt 10.0 Ammonium bromide ioo.

Ammonium nitrate 10-0 bleach accelerator o-oos mol/20.0 Aqueous ammonia (27%) Add water, Omtnot, ob pH 6,3 Bleach-fix solution (Units: Ferric ethylenediaminetetraacetate) Ammonium dihydrate salt !0.0 ethylenediaminetetraacetic acid disodium salt YO, O sodium sulfite / 2. O ammonium thiosulfate aqueous solution (70%), 2≠0, 0 yd ammonia water (, 27%) A, od water all added /,0LpH7,,2 Washing liquid Tap water iH Pear-type strong acid cation exchange resin (Amberlite IR-/J0B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-4Loo) mixed bed Water was passed through the column to reduce the concentration of calcium and magnesium ions to 3 m9/l or less, and then 20 m9/l of sodium dichloride/dag-incyanurate and 0.9 m/l of sodium sulfate were added. The pH of this powder is 6
．． Turf, in the evening range.

Stabilizing liquid (unit y) Formalin (37%) Polyoxyethylene-p-monononylphenyl ether (XF-degree of homopolymerization io) Ethylenediaminetetra-11 acid disodium salt Add 0.0 evening water /, θLp)i
r, 0-g, 0 The obtained sample was subjected to centometry, and the results shown in Table r were obtained.

0.3 2.0ml.

By using the fine particle solid dispersion of the compound of the present invention in the anti-rayon layer, it is possible to obtain a photosensitive material which is free from deterioration in sensitivity, potassium, and residual color after processing, and has a small amount of residual silver. .

hmm centre centre Procedural amendment Display of incidents Heisei/Year Patent Application No. 70376/ name of invention Silver halide photographic material person who makes corrections

Claims (3)

[Claims] (1) A silver halide photographic material characterized by having a hydrophilic colloid layer containing a solid fine particle dispersion of a compound represented by the following general formula (I). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc.
Aryl group, heterocyclic group, COR_4 or SO_2R_4
, R_3 is a hydrogen atom, cyano group, hydroxyl group, carboxylic acid group, alkyl group, aryl group, COOR_4, O
R_4, NR_5R_6, CONR_5R_6, NR_
5COR_4, NR_5SO_2R_4 or NR_5C
ONR_5R_6 (here, R_4 represents an alkyl group or an aryl group, R_5 and R_6 represent a hydrogen atom, an alkyl group or an aryl group), L_1, L
_2 and L_3 each represent a methine group, and n represents 0, 1 or 2. ] (2) The silver halide photographic sensitizer according to claim (1), wherein the compound represented by general formula (I) is substantially water-insoluble at pH 6 or lower and water-soluble at pH 8 or higher. material. (3) Claim (1) or (2) characterized in that the compound represented by general formula (I) does not have a sulfonic acid group or a salt thereof or a salt of a carboxylic acid group as a substituent.
The silver halide photographic material described above.