JPH0437841A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To form a dye layer of dyes which have adequate spectral sensitivity, can make selective dyeing, are easily decolored and eluted by photographic processing and can impart low Dmin by incorporating at least one kind of specific compds. as a solid fine particle dispersion into the above material. CONSTITUTION:This photosensitive material contains at least one kind of the compds. expressed by formula as the solid fine particle dispersion. In the formula, X denotes a hydrogen atom, alkyl group, aryl group, etc.; and Y denotes a carboxy phenyl group; Z denotes a hydrogen atom, alkyl group, cyano group, CONR<3>R<4>, COOR<3>, COR<3>, SO2R<3>, -NR<3>SO2R<4>, etc., L<1>, L<2>, L<3> respectively denote a methine group; Q denotes a phenyl group or heterocyclic group; n denotes 0 or 1. More preferably, at least one kind of the compds. in which the phenyl group expressed by Q is a 4-dialkylamino phenyl group are formed as the sold fine particle dispersion.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inactive and easily decolorized during photographic processing. The present invention relates to a silver halide photographic material having a hydrophilic colloid layer containing a dye to be eluted and/or a hydrophilic colloid layer.

(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, not only will it have harmful spectral effects on other layers, but its effectiveness as a filter layer or antihalation layer will be diminished. However, when a dye-loaded 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 having an opposite charge to the 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 tILLr.

j4 hiro issue, same 4<, /-μ, 3rt issue, same j, J co j,
It is disclosed in No. A9F etc.

In addition, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in JP-A-2003-239939, Ibid. j-/jt,
jJJO No., jl-133331, t J-,2
7r J r@, t3-/979173.

The same J-Takoa/No., European Patent/! AO No. 1, same 7
It is disclosed in AjA7, AjA7, AjA723, AjA7tj7i, AjA7, AjA7, AjA7, AjA7, AjA7, AjA7, AjA7, AjA7, AjA7, AjA7, AjA7, AjA7, AjA7, AjA7, AjA7723, AjA77i7i, AjA799431, World Patent No. 104'79μ, and the like.

In addition, a method of dyeing a specific layer using gold TI4 salt fine particles adsorbed with dye is disclosed in U.S. Patent λ, 7/9, 0♂; JP-A-Sho AO-44. It is disclosed in tJJ No. 7 etc.

However, even with these improved methods, there are problems such as the fact that dye diffusion cannot be completely prevented and the speed of decolorization during development processing is slow. When there are changes in various factors such as improvements in color, there is a problem that the decolorizing function cannot always be fully demonstrated.

[Problem to be solved by the invention]

Therefore, it is an object of the present invention to dye a specific hydrophilic colloid layer in a photographic light-sensitive material, to prevent the dye from spreading, and to quickly decolorize it during the development process, so that the dye dissolved and decomposed into the photographic processing solution is removed. An object of the present invention is to provide a photographic light-sensitive material containing a dye in the form of a solid fine particle dispersion designed not to have any adverse photographic effects.

(Means for Solving the Problems) (1) The objects of the present invention are achieved by a silver halide photographic material containing at least one compound represented by the following general formula (I) as a solid fine particle dispersion.

General formula (1) In the formula, X represents a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, COOR", or CONRIR2, Y represents a carboxyphenyl group or a group having an aliphatic carboxylic acid, and Z represents a hydrogen atom, Alkyl group, cyano group, C0NR
R1 , R2, R3, and R4 are each a hydrogen atom,
Represents an alkyl group or an aryl group.

Preferably, this is achieved by a silver halide photographic material containing at least one compound represented by Q in the general formula (1), which is a phenyl group or a dialkylaminophenyl group, as a solid fine particle dispersion.

Preferably, this is achieved by a silver halide photographic material containing at least one compound represented by Q in general formula (1) as a solid fine particle dispersion. (In the formula R1
1, R12, R13, R14Vi.

Each represents a hydrogen atom, an alkyl group, or an aryl group. ) Next, the general formula (summer) will be explained in more detail.

The alkyl group represented by
butyl) or a substituted alkyl group (e.g. carboxymethyl, ethoxycarbonylmethyl, benzyl), the aryl group represented by Unsubstituted 7-aryl group (e.g. phenyl) or substituted aryl group
group (9'lJt 4'-methoxyphenyl, μm chlorophenyl, μ-carboxyphenyl) AE is preferred.

The carboxyphenyl group represented by Y is q-carboxyphenyl, 3-carboxyphenyl, -1-carboxyphenyl, 3. j-nkar〆quinphenyl! Preferred are -carboxycometquinphenyl, j-carboxy-hydroquinphenyl, 3゜j-dicarboxyquinphenyl, etc. The group having an aliphatic carboxylic acid represented by Y is an alkyl group having a carboxylic acid. (e.g. carboxymethyl, Preference is given to aryl groups with aliphatic carboxylic acids (for example .mu.-carboxymethoxyphenyl, .mu.m(J--h carboxyethoxy)phenyl).

The alkyl group represented by Z is preferably an alkyl group with a carbon number of 1 to .
Ethoxycarbonylmethyl, cohydroxyethyl) are preferred.

Each of the methine groups represented by L 1 , L 2 , and R3 is preferably an unsubstituted methine group, but substituents (such as methyl,
Henshil).

The phenyl group represented by Q has the general formula μ-(N-x thyl-N-β-hydroxyethylamino)
-11 methylphenyl is preferred. Gualkoxyphenyl groups are preferred, such as ≠-methoxyphenyl, and Q
A phenyl group U- or 3. ≠-methylenedioxyphenyl and ←-butoxyphenyl are preferred.

In the above formula, B21R22, H23, R24, R25, R2
6 represents a hydrogen atom, an alkyl group, or an alkoxy group. Q
Preferably, the nophenyl group represented by the formula is, for example, gauge methylaminophenyl, nocarboxy-μm dimethylaminophenyl, μm dimethylamine-methylphenyl, Hiro-(N-ethyl-N-β-methanesulfonamidoethylamino)-11 Methylphenyl is preferred, where R1!
, R12, R13 and R14 each represent a hydrogen atom, an alkyl group or an aryl group. Each of the alkyl group and aryl group may have a substituent.

The alkyl group represented by R11, R12, R13, and R14 is preferably an alkyl group having from 1 to 10 carbon atoms, and an unsubstituted alkyl group (for example, methyl, ethyl, butyl, +2-
ethylhexyl, cyclohexyl) or substituted alkyl groups (e.g. λ-hydroxyethyl, carboxymethyl,
dimethylaminoethyl) is preferred, R11, R12,
The aryl group represented by R13 and R14 is preferably an aryl group having t to 10 carbon atoms, and is an unsubstituted aryl group (e.g. phenyl, naphthyl) or a substituted aryl group (e.g. 3-carboxyphenyl, j-carboxy-2-methoxyphenyl). , !-hydroxycohydroxyphenyl, μm dimethylaminophenyl, q-ethoxycarbonylphenyl) are preferred. Further, R and R may form a t-membered ring.

The alkyl groups represented by R1, R2, R3, and R4 may have a substituent, and preferably an alkyl group having 7 to 10 carbon atoms (fat is methyl, ethyl, butyl, -monoethylhexyl). ) or substituted alkyl groups (e.g. cochloroethyl, -monohydroxyethyl,
λ-Methanesulfonamidoethyl, -monoacetamidoethyl, -monocarboxyethyl, Co-N,N-dimethylaminoethyl%-monoethoxyethyl, carboxymethyl,
Ethoxycarylmethyl, allylbenzyl, methoxysulfonylethyl) are preferred, and 1 (1 and R2
, R3 and R4 may form a ring (! or a t-membered ring is preferred).

The aryl group represented by R1, R2, R3, R4 may have a substituent, and an aryl group having a carbon number of t to 70 is preferable, an unsubstituted aryl group (for example, phenyl) or a substituted aryl group (for example, 2.j-dichlorophenyl, V-methylphenyl, g-hydroxyphenyl, t-
cyanophenyl, sulfamoylphenyl)
stomach.

Among the compounds represented by the general formula (1), those in which X is a hydrogen atom or a methyl group and Z is a cyan group or a carbamoyl group are particularly preferred.

In addition, the compound represented by general formula (1) is X, Y, Z, H
One molecule of the groups represented by 1, B2, R3, R4, R5, and R6 may be bonded to form a monomer.

Next, specific examples of the compound represented by the general formula (1) will be shown, but the present invention is not limited thereto.

l3 1 da/j CH2C12CH2CH2CH2C0OH/j CH2CH2CH2CH2CH2C0OHCH3 0OH CυUH -! Kot 3 cores 3μ L; (, KJI-1 3t ShiriUh Dako μμ OOH μO C:CX) H daj ■ μ7 OOH l! O data These compounds can be synthesized according to the method described in JP-A Shoyoj-/jjJJ/.

Synthesis Example 1 (synthesis of compound /) /-(≠-carboxyphenyl)-J-Schiff, /-t-
Hydroxy-goomethylpyridocone 27.0g%
p-dimethylaminocinnamaldehyde/7. A mixture of Jg, 1 methanol, and 00 mL was heated under reflux for 30 minutes. After cooling to room temperature, the precipitated crystals were collected and dried to obtain Compound 1, JJ', □g.

green powder. λIii! I\z A / j nm, melting point 3oo'c or more.

Synthesis example (synthesis of compound l/) /-(co(3-carboxy-!-norbornen-ylcarbonyloxy)ethyl) -j -cyano-6
-Hydroxig = methylpyrido λone 9.0g, p
A mixture of -dimethylaminocinnamaldehyde, +itg, and 100 mL of methanol was heated under reflux for 30 minutes.

After cooling to room temperature, one of the precipitated crystals was taken and dried to obtain 10.9 g of compound //. λ product section t/Onm, melting point 201-
．． 20 QC0 synthesis example 3 (synthesis of compound 3q) 3-carbamoyl-/-(!-carboxyphenyl)-
t-Hydroxy-Hiro-methylpyridocone? , (I
g,/-(II-dimethylaminophenyl)-J-formyl-,2,j-)Jfruhirol? , Og, X
A mixture of tanol q Om L/.

The mixture was heated under reflux for 5 hours. After cooling to room temperature, the precipitated crystals were collected and dried to obtain compound 3μ.

I got Ig. Melting point -jr~-2μ00 The compound of general formula (I) is used in an amount of 7 to 1000 mg per m2 of area on the photosensitive material, preferably //m2/-
, 100 mg is used.

When using the compound of general formula (I) as a filter dye or antihalation dye, any effective f can be used, but the optical density is 0°0! It is preferable to use it within the range of J to j. The addition time may be any step before coating.

The compound of general formula (1) 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 the general formula (1) of the present invention can be prepared by a method of precipitating the compound of the present invention in the form of a dispersion and/or by a known grinding means such as Ball Mill I in the presence of a dispersant.
Using a method of forming by J (ball mill, vibratory 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.] can be formed. 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 microcrystalized 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 gm or less, particularly preferably 0.5 μm or less, and in some cases 0.5 μm or less. It is more preferable that the particles be fine particles of 1 pm 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, tin 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.
For example, it may be a negative-tone emulsion), or it may be a grain that is mainly formed inside the grain (for example, an internal latent image type emulsion, a pre-fogged direct reversal type emulsion), and 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. The coefficient of variation above (in the distribution expressed by the diameter when the projected area is approximated as a circle, the Itl deviation S divided by the diameter d (t! S / d) is 20%
The following monodisperse emulsions are preferred, and tabular grain emulsions and monodisperse emulsions of 211 or more may be mixed.

The photographic emulsion used in the present invention is B. gelafchides (P
, GIafkldei), Shimmy Engineering Physique
Photographic (Chis+ie er Phys
iquePhoLographeque) (Paul Montell, 1967), G.F. Duffin (
G.F. Duffin), Photographic Emulsion Chemistry
Emulsion Chemistry) (Focal Press, 1966), Making and Coating Photo by V, L, Zallksan et al.
graphic emulsion) (Focal Press, 1964).

During the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (eg, U.S. Pat. Nos. 3,271,157 and 3,574) are used as silver halide solvents to control grain growth. 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. 53-02408, 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 sulfate esters; 111 conductors such as sodium alginate and starch derivatives; polyvinyl alcohol and polyvinyl alcohol moieties Acetal, poly-N-vinylpyrrolidone,
Various synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

As for gelatin, in addition to general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japanese Society of Scientific Photography ([1ull.

Soc, Sci, Phot, Japan), l
Enzyme-treated gelatin may be used as described in 'kL16.30 (1966), or a hydrolyzate of gelatin may be used.

In the photosensitive material of the present invention, inorganic or organic F is added to any hydrophilic colloid layer constituting the photographic photosensitive layer or the back layer.
For example, chromium salt,
Specific examples include aldehyde R (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol compounds (dimethylol urea, etc.). Active halogen compound (2,4-dichloro-6-hydroxy-
1,3゜5-triazine and its sodium salt, etc.) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propatol, II 2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether or N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinium) are preferable because they quickly harden hydrophilic colloids such as gelatin and give stable photographic properties. ) methanesulfonate, etc.) and haloamidinium salts (1-(1-chloro-1
-pyridinomethylene) pyrrolidinium-2-naphthalenesulfonate, etc.) are also excellent in their fast curing speed.

The halogenated radiographic emulsion used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, Included are hemicyanine dyes, styryl dyes and hemioxokyl 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 pigments can be applied to these pigments as a base bioheterocyclic nucleus. 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, 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 complex merocyanine dyes have ketomethylene structures such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2,
5-6jiJ such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl #i nucleus, etc.
An i-node 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 enhancing 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. Aminostilbene compounds which are ring nuclei and are substituted (for example, U.S. Pat. Nos. 2,933,390 and 3,635°721)
U.S. Pat. No. 3,6615.613, which may include aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, etc. ,615
．． No. 641, No. 3.617.295, No. 3,635.
The combinations described in No. 721 are particularly useful.

The side of the silver halide photographic hole used in the present invention has the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance.
Various compounds can be included. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazole necks, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-pheny/L/-5-mercaptotetrazole), etc.; mercaptovirimidines; mercaptotriazines 1 Thioketo compounds such as oxadorinthion; azaindenes, e.g. triazaindene; kind,
Tetraazaindene wA (especially 4-hydroxy fA (
1゜3.3a, 7) Tetraazaindene [), pentaagoindenes, etc.; many known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. compounds can be added.

The photosensitive material of the present invention can be used as a coating aid, to prevent 11F electrostatic discharge, to improve slipperiness, to emulsify and disperse, to prevent adhesion, and to improve photographic properties (for example, to accelerate development, to make Vl!llI, to sensitize, etc.). It may also contain an agent.

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 arrangement of the eyebrows is, from the support side, in the order of red sensitivity, green sensitivity and blue sensitivity, blue sensitivity layer, green sensitivity layer and red sensitivity layer, or blue sensitivity, red sensitivity and green sensitivity in this 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 degree of attainment.
The layer structure may further improve the graininess.

Furthermore, a non-light sensitive layer may be present between two or more emulsion layers having the same color sensitivity, or an emulsion layer having a different color sensitivity may be inserted between certain emulsion layers having the same color sensitivity. The sensitivity may be improved by providing a reflective layer such as fine grain silver halide under the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer.

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 milk 7FIJ layer contains a yellow-forming coupler, but different combinations may be used depending on the case. For example, by combining an infrared-sensitive layer, it may be used for 1M4Q color photography 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. Those used as flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate, baryta layers, or α-olefins. Paper coated with or laminated with a polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

The surface of these supports, which may be black for the purpose of blocking light, is generally subjected to a subbing treatment to improve adhesion with photographic emulsion layers and the like. The support surface is coated before or after priming.
Glow discharge, corona discharge, ultraviolet & j! 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, Sou 17123 (
(July 1978) or by utilizing a trichromatic coupler mixture as described in U.S. Pat.
The present invention can also be applied to black-and-white photosensitive materials for X-rays by using the black-coloring couplers described in British Patent No. 2.102.136 and British Patent No. 2.102.136. 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, C0M or regular microfilm, silver salt diffusion transfer type photosensitive materials, and The present invention can also be applied to print-out type photosensitive materials.

When the photographic element of the present invention is applied to color diffusion transfer photography,
-16356, 4B-33697, JP-A-1983-
13040 and British Patent No. 1,330.524, or a peel-free type film unit as described in JP-A-57-119345. I can do it.

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 negative phase, or it may be sealed in a processing liquid 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 proof 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.

A gas, a dye, that emits light in a wavelength range from ultraviolet to infrared.
Solution or semiconductor lasers, light emitting diodes, and plasma light sources can also be used as recording light sources. In addition, linear or surface phosphor arrays using phosphor screens (CRT, etc.), liquid crystals (LCD), and lanthanum-doped lead titanium zirconate (PLZT) emitted from phosphors excited by electron beams, etc. It is also possible to use an exposure means that combines two light sources. 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. Although amine phenol compounds can be used as the color developing agent, p-phenylenediamine compounds are preferably used, and representative examples include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and P-)luenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it includes such things as 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, viscosity-imparting agents, Various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, West German patent ratio @
(OLS) No. 2,622,950, etc. may be added to the color developer.

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, l-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known black and white developers such as aminophenols such as methyl-p-7 minophenol can be used alone or in combination.

Not only a color developing solution but also any photographic developing method may be applied to the photosensitive material of the present invention.As the developing agent used in the developing solution, a dihydroxybenzene-based developing agent, 1
-Phenyl-3-pyrazolidone type developing agents, p-aminophenol type developing agents, etc., and these can be used singly or in combination (for example, l-phenyl-3-pyrazolidones and dihydroxybenzenes, or p-aminophenols and dihydroxybenzene). ) 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 bisulfite and hydroquinone.

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

Compounds that provide free sulfite ions as preservatives in the developer, such as sodium sulfite, potassium sulfite, meta-potassium sulfite,! i! Ir! Sodium sulfate etc. are added. In the case of an infectious developer, Htlumaldehyde sodium bisulfite may be used, which provides very little free i-sulfate ion 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, such as azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, Bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole R
(especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines frequently; mercaptotriazines, such as thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy (1, 3, 3
a.

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

The developing solution that can be used in the present invention may contain the same polyalkylene oxide as described above as a development inhibitor. It can be contained within the range of.

The developer that can be used in the present invention includes nitrilotriacetic acid, ethylenediaminetetraacetic acid, and triethylenetetraamine as water softeners.

It is preferable to add xaacetic acid, diethylenetetraamine interacetic acid, and the like.

The developer used in the present invention includes a compound described in JP-A-74-1-G3≠7 as a silver stain preventive agent, and a compound described in JP-A-1988-1983 as a development unevenness preventive agent. ,
As a solubilizing agent, the compounds described in Japanese Patent Application No. 70-70-3 can be used.

The developing solution used in the present invention contains JP-A-Sho T as a buffering agent.
Boric acid described in Ko/lt Koj No., JP-A-Sho tO-93
Saccharides (e.g. saccharose), oximes (e.g. acetoxime), phenol Ij described in No. 4tJJ
(eg, !-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), etc. are used.

Various compounds may be used as the development accelerator used in the present invention, and 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, mesoion 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 necessary to add them to the photosensitive material. You can also do it. 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. The organic amine can be an aliphatic amine, an aromatic amine, a cyclic amine, a mixed aliphatic-aromatic amine or a heterocyclic amine; 11 secondary and tertiary amines and quaternary ammonium compounds are all useful. .

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

The bleaching process may be carried out simultaneously with the fixing process or separately.In order to further speed up the process, a bleaching process may be followed by a bleach-fixing process.As a bleaching agent, for example, iron may be used. (■), cobalt (■), chromium (I
Typical bleaching agents include ferricyanide; dichromate; iron (II)
I) or 41!11 salts of cobalt (IIN), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propatoltetraacetic acid, or citric acid, tartaric acid, Complex salts of organic acids such as malic acid; persulfates; manganates; nitrosophenols, etc. can be used. Among these, iron(III) salt of ethylenediaminetetraacetate, iron(III) diethylenetriaminepentaacetate (I[I
) salts and persulfates are preferred from the standpoint of rapid processing and environmental pollution, and the ethylenediaminetetraacetic acid iron(I[[) complex salts 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. Pat. No. 3,893,858;
．． No. 290.812, No. 2,059°988, JP-A No. 63-32736, No. 53-57831, No. 374
No. 10, No. 53-65732, No. 53-72623, No. 53-95630, No. 53-95631, No. 5
No. 3-104232, No. 53-124424, No. 53
-141623, 53-28426, Research
Compounds having a mercapto group or disulfide group as described in Disclosure No. 8117129 (July 1970); Thiazolidine derivatives as described in JP-A-50-140129; JP-A-45-8506, JP-A-52- No. 20832, No. 53-32735,
Thiourea derivatives described in U.S. Pat.
Iodide recorded in No. 6235; West German Patent Box 966.410
Polyethylene oxides described in Japanese Patent Publication No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication No. 49-42434 and Japanese Patent Publication No. 49-5
No. 9644, No. 53-94927, No. 54-3572
No. 7, No. 55-26506 and No. 5B-16394
The compound described in No. 0 and iodine and bromide ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in US Pat. No. 3,893,858 and West German Patent Box 1290.81.
No. 2, JP-A No. 53-95630 is preferred, and the compounds described in U.S. Pat. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for use in photosensitive materials.

Examples of the fixing agent include thiosulfates, thiocyanates, thioureas of thioether compounds, and a large amount of iodides, but thiosulfate salts 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. In the water washing process and stabilization process, various known compounds may be added for the purpose of preventing precipitation and saving water.9 For example, to prevent precipitation, inorganic phosphoric acid, aminopolycarboxylic acid, organic amino Water softeners such as polyphosphonic acid and organic phosphoric acid, disinfectants and anti-piping agents that prevent the growth of various bacteria, algae, and mold, metal salts such as magnesium salts, aluminum salts, and bismuth salts, or dry loads. A surfactant for preventing unevenness and various types of V1 film removal can be added as necessary. Or Photographic Science and Engineering magazine by West (L, U, We
It is also possible to add the compounds described in ``St.

In the washing process, two or more layers are generally flushed with water to save water. Furthermore, instead of the water washing process,
A multi-stage countercurrent stabilization process as described in No. 8543 may be implemented.In the case of a 0-unit process, 2 to 9 countercurrent baths are required.In the 0-unit stabilization bath, the above-mentioned addition In addition to the agent, various compounds are added for the purpose of stabilizing the image. For example, Il
! Various buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide) for adjusting IpH (e.g. pH 3-9);
Typical examples include ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.), and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, amoborisulfonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (benzisothiazolinone, irithiazolone, 4- Thiazoline, benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactant, optical brightener, hardener, etc. 1 each! Additives may be used, and two or more compounds for the same or different purposes may be used in combination.

Mata, JIIp H after processing! It is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a regulating agent.

In addition, for color photosensitive materials for imaging, the normally performed post-fixing (washing - stabilization) process can be replaced with the above-mentioned stabilization process and washing process (water saving process).In this case, the magenta coupler is In this case, 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. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent.

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 Schiff base type compounds described in JP-A No. 13924, aldol compounds described in US Pat. No. 13924, metal salt complexes described in US 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 light-sensitive material of the present invention may contain various 1-phenyl-
Typical compounds that may contain 3-pyrazolidones are JP-A Nos. 56-64339, 57-144547, 57-211147, 5B-50532, 5B-50536, and 5B. -50533, 58-
No. 50534, No. 5B-50535 and No. 5-1
It is described in No. 15438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. A temperature of 33'C to 38C 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 nodal lines of the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2.226.770 or US Pat. No. 3.674499 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 one-percent color photographic material, it can be bleach-fixed as required, very generally, and when it is a color photographic material for photographing.

(Example) Next, the present invention will be specifically explained.

Example-7 The following formulation - 1st undercoat layer and formulation - on both sides of a biaxially stretched polyethylene terephthalate support with a thickness of 100μ
The first layer of undercoat (2) was applied in sequence.

Prescription - ■ First layer of undercoat Copolymer of vinylidene chloride/methyl methacrylate/acrylonitrile/methacrylic acid (90/I/1//weight ratio) l! Weight part J, 4Z-dichloro-4-hydroxy-s-triazine 0,
J, parts by weight of polystyrene fine particles (average particle size 3μ) o, oz compound -■
θ,,2゜Add water
Add 100% IIC, 10% by weight KOH, p
The H=AK-adjusted coating solution was applied at a drying temperature of i1o 0c for 2 minutes so that the dry film thickness was 0.9 μm.

Compound - 〇 Water was added to ioo parts by weight. This coating solution was dried at a temperature of 7 o 0 c for a minute until the amount of gelatin was a,
/Ag/m2.

Compound-〇aSeα Compound-■ Prescription-■ Undercoat second layer gelatin methylcellulose compound-■ Cl2H250 (CH2CH20)1oH compound-■
3 1 part by weight of acetic acid O, Oj 0. 0.2 O,O3 X1O-3 0,+2 The following formulation -
A conductive layer and a pack layer of ■ and -■ were applied.

Prescription-〇 Conductive layer 8n02/Sb (9/i weight ratio, average particle size 0,
．． 2jp) 300mg/m2 gelatin
/70 70-■ 7 mg g/m
2 Dotecylbenzenesulfonate sodium salt 10 Dihexyl α-sulfosuccinate sodium salt Gθ Polystyrene sulfonate sodium salt 9 Prescription - ■ Pack layer gelatin /, rg/m2 compound - 700 mg / m2 compound -
■ 60 Compound-〇 10 Compound-■ t Dotecylbenzenesulfonic acid sodium salt jO Dibenzyl-α-sulfosuccinate sodium salt i.

11.2-bis(vinylsulfo) nylacetamido)ethane lo.

Ethyl acrylate latex (average particle size 0.0jμ) 300mg/m2, e
Fluorooctane sulfonic acid lithium salt 7 Silicon dioxide fine powder particles 3! (Average particle size μ, pore diameter/7d, surface area 300m27g) Furthermore, the following coating was applied to the opposite surface.

Compound-〇700mg/m2 Compound-■! Omg/m2 of compound-! Omg/m2 Emulsion A was prepared using the following solutions I, ① and ② by the following method.

■Liquid: 100ml of water! Gelatin/rgpH3.

■Liquid: AgNO3200g Water r00ml ■Liquid: K
Br/, Referenceg Naα7Ag(NH4)3Rhα61
1mg water f00ml) Emulsion A (Br1 mole particle size 0.JOp Rhi, oxio-5 mole 1 mole Ag) IIo Add solutions 1 and 2 to solution I maintained at 0cVc,
The addition was carried out at a constant speed over a period of 20 minutes with simultaneous mixing on both sides. This emulsion was prepared using a conventional method well known in the art.
After removing soluble salts, gelatin was added as a stabilizer without chemical ripening, and comethyl-q-hydroxy-/, J, J
a, 7-thitraazaindene was added. The average grain size of this emulsion was O.mu., the yield of the emulsion was /kg, and the amount of gelatin contained was tag. An emulsion was prepared by adding a hydrazine compound (Hz) to this emulsion in an amount of ≠X10-2 moles and 1 mole of Ag.

After adding 100 mg/m2 of ultraviolet absorber (UV absorber), 30 wt% of polyethyl acrylate latex was added based on solid content of gelatin.
As a hardening agent, /, added J-bis(vinylsulfonyl)-coprohanol, 2.5 g 7 m2 of Ag on t, yp solyethylene terephthalate film, gelatin /,
/Ig/m2.

A protective layer of 0.9 g/m2 of gelatin is applied to this upper layer.
Sample /-/ was created.

Furthermore, samples l-λ to /-7 were prepared in which a yellow dye was added to the protective layer as shown in Table 1.

For samples /-μ to /-7, solid dispersions were used as the dyes dispersed as follows. Water (4ZJ44r+J)')jt
-(j Triton
8) (sold by Rohm & Hass) 6.
20 g of dye and beads of zirconium oxide were added to the 7-day solution and the contents were ground in a ball mill for V days. The zirconium oxide beads were later removed by filtration.

Table 1 Protective layer of each sample (equivalent to the compound of JP-A @zz-/jz, iti issue (10/))
P-t07 Ultra-high pressure mercury lamp ORC-CHM-ioo
Adjust the exposure amount by applying a neutral density filter (ND filter) using O. Expose each sample so that the exposure time is the same for each sample using K, and use the following developer A.
Fuji Photo Film ■ automatic developing machine FG-3toPTs
3r oct seconds processing (Dry-1o-Dry
(about 10 seconds). Note that 0R-F/ was used as the fixing solution.

Developer A Hydroquinone 41j, 0gN-
Methyl-p-aminophenol/cosulfate 04g Sodium hydroxide, 0g Potassium hydroxide
Hello, Og! -Sulfosalicylic acid
tit, 0g boric acid +
2j, 0g potassium sulfite/10.
Og ethylenediaminetetraacetic acid dinato 2-norum salt
/ , θ g potassium bromide
1. Og! -Methylbenztriazole
0. Ign-butyl-getanolamine/j, Og Add water/l (pH=/ /, A) The prepared samples /-/~/-7 were evaluated for color retention and safelight safety. Ta.

(11 Evaluation of residual color photographic material /-/-/-7 was subjected to the automatic processing described above without exposure. The residual color after processing was sensory evaluated and the results are summarized in Table 2. .

The following level classification was applied as evaluation criteria.

◎...No residual color bothers me at all.

○: There is a slight residual color, but there is no practical problem.

×...I'm concerned about residual color. There are practical problems.

Z...The residual color is very bad. It cannot be put into practical use.

(2) Safelight safety evaluation Toshiba fluorescent lamp (1; "LR Ge08W") wrapped with l'lc and tg swilter, irradiated for 1 hour under approximately θO lux, then developed, and the fog density at that time was evaluated. We measured the increase in

Table 2 Results As is clear from Table 2, sample 16 of the present invention, /-
It can be seen that 7Vi has excellent color retention and is also superior in safelight safety, reliably suppressing safelight fog even in a smaller amount than samples /-λ and /-3 using water-soluble dyes.

Example - Preparation of a support A biaxially stretched blue-dyed polyethylene terephthalate film with a thickness of 7 μm was treated with di-coron and coated on both sides with a wire bar coater to the following coating amount. , /7J for 1 minute at 0C.

・Butadiene-styrene copolymer latex Butadiene/Methi2F weight ratio = 3// 69 a, /1g/rn2・co,
Hiro-dichlorot-hydroxy-5-) riazine sodium salt da, λmg/m2*In the latex solution, nc6H1300c is used as an emulsifying dispersant.
Contains cH2nc6H1300ccH-8O3Na in an amount of 03wt% based on the latex solid content.

On top of this, coat both sides with a wire bar coater to the following coating amount, /7! It was dried at 0C for 7 minutes.

・Gelatin AOmg/m2 (n
=r, j) 0.4mg/rr+! Furthermore, the following coating amount was applied on this using a wire bar coater, and the coating was dried at /7J 0C for 1 minute.

O Zera f:y /J7mg/m2
・Dye of the present invention/AOmg/m2/
, t 7mg/m2 ・Matting agent −, j j mg /
m2 In the preparation of a polymethyl methacrylate support with an average particle size of -1 j μm, the dye of the present invention was used as a dye having the following structure (corresponding to the compound (10) of JP-A-Shojj-/!j, No. 3!/). ) to obtain a support.

(Dye ■) CH2CH20H Preparation of dye liquid The dye liquid was dispersed in water with a surfactant using a ball mill, as in the preparation of the /-47-/-7 sample in Example 1.
A liquid in which solid dye was dispersed was obtained.

Preparation of Emulsion Layer Coating Solution In 1 liter of water, 1 g of potassium bromide and 0.0 g of potassium iodide were added. Ojg, gelatin 30g, thioether HO(CH2)28(0(2)28(CI(2)20H
(D J'A aqueous l-2, ICC added and 73°
Add silver nitrate 1, JJg into the solution maintained at C while stirring.
and the bromide power IJ j .

An aqueous solution containing 72 A g (μg, iodizing power') was added in qj seconds by a double jet method. Subsequently, after adding calico bromide, jg, the amount of silver nitrate r, 3
An aqueous solution containing 3 g was added over 7 minutes and 30 seconds so that the flow rate at the end of the addition was one times that at the start of the addition. Subsequently, an aqueous solution of 1jJ of silver nitrate, 317g, and a mixed aqueous solution of potassium bromide and potassium iodide were added in Jj minutes by a controlled double jet method while maintaining the potential at pAg#,/. The flow rate at this time was accelerated so that the flow rate at the end of addition was twice the flow rate at the start of addition. After the addition was completed, a 2N potassium thiocyanate solution/j CC was added, and then 1 h of an aqueous potassium iodide solution j OCC was added over 30 seconds.

After that, the temperature was lowered to 3j0C and soluble salts were removed by the sedimentation method, and then the temperature was raised to ao0C and gelatin 6r
g and phenol-gl trimethylolpropane 7.7
g, and the pH was adjusted to 4, tr with sodium chloride and potassium bromide.
, pAgr, was adjusted to 10.

After raising the temperature to t+'c,
Methyl-/, J, Ja, 7-chitrazaindene 17m
g and 425 mg of a sensitizing dye having the following structure were added. Sodium thiosulfate j hydrate j, jmg Potassium thiocyanate/AJmg after io minutes.

Chloroauric acid J and Amg were added, and 3 minutes later, the mixture was rapidly cooled and solidified. The resulting emulsion has 93% of the total projected area of all grains.
However, the ass is composed of particles with a kuto ratio of 3 or more, and the aspect ratio is −
The average projected area diameter for all the above particles is 0
．． 9! μm, standard deviation 3 cm, average thickness is o, izz
The aspect ratio in μm was A,/.

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

-J, 4-bis(hydroxyamino)-μm diethylamino i, 3. z-triazine
IOmgQ sodium polyacrylate (average molecular weight μ, 10,000), OgH, copolymerized plasticizer with a composition ratio of ethyl acrylate/acrylic acid/methacrylic acid = RI/J/J and nitrone 20. 0g 10mg 2H5 2H5 j, Omg Preparation of Photographic Material Co/, λ-1 The above emulsion layer coating solution was applied to the support 1. - were coated in the same manner on both sides to obtain photographic materials-1/, 2-2. At this time, the amounts of the emulsion layer and surface protective layer coated on one side were as follows.

<Emulsion layer> -Amount of silver coated /, 9g/m2 -Amount of gelatin coated /, 1g7m2 <Surface protection layer> - Gelatin o, (rtg/m2
Dextran (average molecular weight 39,000) 0.1/g/m2 Sodium polyacrylate (average molecular weight!,/10,000) 2omg7m2f [ll
Corbis(vinylsulfonylacetamido)ethane was applied at a rate of j A mg/m 2 per side.

- Matting agent (average particle size J, jμm) Copolymer of polymethyl methacrylate/methacrylic acid = 9//0. OAg/m2 HA Omg 7m2 20mg/m2 ・C4F17S02N(CH20-120)4(CI-
42) 4SO3Na・C3F17802N (c) I2C
) (20), 5H3H7 j mg/m2 -da-hydroxyt-methyl-1/, 3.3a, 7 tetrazaindene/j, jmg/m2 Evaluation of photographic performance Photographic materials include Fuji Photo Film GRENEX Orthoscreen HR-a was brought into close contact with both sides using a cassette, and X-ray sensitometry was performed. The exposure amount was adjusted by changing the distance between the X-ray tube and the cassette. After exposure, processing was performed using an automatic processor using the following developer and fixer.

Dry to Dry processing time: +, 1 second The developer and fixer used had the following compositions.

(Developer) Potassium hydroxide Kota g Potassium sulfite Gugu, J g Sodium hydrogen carbonate 7.1 g Boric acid
/, 0g diethylene glycol ethylenediaminetetraacetic acid! -Methylbenzotriazole hydroquinone glacial triethylene glycol acetate! -Ditroindazole l-phenyl-3-pyrazolidone geltaraldehyde (70w17wt%) Add sodium metabisulfite potassium bromide water (fixer) Ammonium thiosulfate (70wt/vo1%) Disodium ethylenediaminetetraacetic acid diwater Sodium sulfite boric acid/Jg/, 7g O, OAg, 2! g /, rg /ug O, Jjg, 2. Irg 6g 12.7g 3.7g /, Ol 200ml 0.02g 11g 0g Sodium hydroxide &, 7g Glacial acetic acid /jg Aluminum sulfate 10g Sulfuric acid (JAN)
Add 3.9g water to make total volume/l.

(pH adjusted to μ, -!) Measurement of residual color After the unexposed film was subjected to the automatic development process described above, it was processed using X-Rite 3/0 (The
The green transmitted light density was measured using a density meter manufactured by Company. On the other hand, the green transmitted light density of the unprimed blue-dyed polyethylene terephthalate support was measured, and the net value obtained by subtracting this value was evaluated as the residual color density value.

Measurement of sharpness (MTF) The MTF was measured using the combination of the above HR-t, t screen and automatic processor processing. 30μmXj00pm
7. It was measured with an e-Cure, and the optical density was evaluated at the part where the optical density was / and 0 using the MTF value at a spatial frequency of / and 0 cycles/mm.

Table 3 From Table 3, it can be seen that the present invention provides a light-sensitive material in which the dye is quickly decolorized and has excellent residual color.

(Effects of the Invention) In the silver halide photographic material containing the compound of the present invention, the dye in the dye layer has appropriate spectral absorption, the dye layer can be selectively dyed, and it can be easily decolorized by photographic processing. , and has the excellent effect of providing low l)min.

Further, the silver halide photographic material of the present invention provides images with improved sharpness without reducing sensitivity, and is stable even during long-term storage without deterioration in photographic performance.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 4. Target of correction “Detailed description of the invention J” in the specification column Display of incidents name of invention 3. Person making the amendment Relationship with the incident 1990 patent application No. 1 No. 45833 Silver halide photographic material

Claims (3)

[Claims] (1) A silver halide photographic material comprising at least one compound represented by the following general formula (I) as a solid fine particle dispersion. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, COOR^1, or CONR^1R^2, and Y
represents a carboxyphenyl group or a group having an aliphatic carboxylic acid, Z is a hydrogen atom, an alkyl group, a cyano group, a C
ONR^3R^4, COOR^3, COR^3, SO_
2R^3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -NR
^3SO_2R^4 or represents a nitro group, L^1, L
^2 and L^3 each represent a methine group, Q represents a phenyl group or a heterocyclic group, n represents 0 or 1, R^1
, R^2, R^3 and R^4 each represent a hydrogen atom, an alkyl group or an aryl group. (2) The silver halide photographic material according to claim 1, wherein the phenyl group represented by Q in general formula (I) is a 4-dialkylaminophenyl group. (3) The silver halide photographic light-sensitive material according to claim 1, wherein the heterocyclic group represented by Q in the general formula (I) is represented by a mathematical formula, a chemical formula, a table, etc. (In the formula R^1^1, R^1^2, R^1^3, R^
1^4 each represents a hydrogen atom, an alkyl group, or an aryl group).