JPH037930A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To selectively dye only a desired layer without adversely affecting the emulsion and to improve the decolorability by photographic processing by incorporating a dispersion of solid fine particles of a specified dye. CONSTITUTION:This sensitive material has a hydrophilic colloidal layer contg. a dispersion of solid fine particles of a dye represented by formula I or II. In the formulae I, II, R1 is alkyl, aryl, cyano, etc., R2 is H or alkyl, each of R3 and R4 is H, alkyl, aryl, etc., R5 is H, alkyl, alkoxy, etc., Q1 is a benzene or naphthalene ring, Y1 is free carboxylic acid, sulfamoyl or sulfonamido, each of L1-L3 is methine, m is 1 or 2, n is 0 or 1, p is 1-3 and q is 0-2. A compd. represented by formula III may be used as the dye represented by the formula I and a compd. represented by formula IV as the dye represented by the formula II.

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 or other 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 provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.

Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, such as in a zero-layer color light-sensitive material, the filter layer may be located between them.

It is based on the fact that light scattered during or after passing through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material opposite to the emulsion layer, and enters the photographic emulsion layer again. Between the photographic emulsion layer and the support, for the purpose of preventing image blurring, that is, halation,
Alternatively, a colored layer may be provided on the opposite side of the support from the photographic emulsion layer. In the case of a zero-layer color photosensitive material, such a colored layer is called an antihalation layer.
An antihalation layer may be placed between each layer.

Furthermore, in X-ray photosensitive materials, a colored layer may be provided as a loss-over cut filter to reduce crossover light and to improve sharpness.

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 layers to be colored often consist of hydrophilic colloids, and therefore dyes are usually incorporated into the layers for coloring. This dye must satisfy the following conditions.

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

(2) It is photochemically inert, that is, it does not adversely affect 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) Although it is decolored during the photographic processing process, it is dissolved and removed and does not leave any harmful coloring on the photographic material after processing.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and the following dyes are known, for example British Patent Nos. 506°385 and 1,17.
No. 7.429, No. 1,311.884, No. 1,338
, No. 799, No. 1゜385.371, No. 1,467.
No. 214, No. 1.433, No. 102, No. 1,553.5
No. 16, JP-A No. 48-85, 130, JP-A No. 49-114
゜No. 420 ζ No. 50-147, 712, No. 55-16
1.233, 5B-143,342, 59-3
No. 8,742, No. 59-111,641, No. 59-1
No. 11,640, U.S. Pat. No. 3,247.127, U.S. Pat. No. 3,469.985, U.S. Pat. , No. 533, 472, No. 3
, 379°533, other oxonol dyes described in British Patent No. 1,278.621, British Patent No. 5
No. 75.691, No. 680,631, No. 599.62
No. 3, No. 786.907, No. 907゜125, No. 1
, 045.609, U.S. Pat. No. 4.255.326, JP-A-59-211.043, etc.;
247, British Patent No. 2.014,598, British Patent No. 750
．． Azomethine dyes described in US Pat. No. 031, etc., anthraquinone dyes described in US Pat. No. 2,865,752, US Pat.
No. 41, No. 2,538,008, British Patent No. 584,
No. 609, No. 1,210,252, Japanese Unexamined Patent Publication No. 50-40
, No. 625, No. 51-3゜623, No. 51-10.9
No. 27, No. 54-118.247, Special Publication No. 48-3,
286, No. 59-37,303, etc.-Redene dye, Japanese Patent Publication No. 28-3,082, No. 44-1
6.594, styryl dyes described in 59-28,898, etc., British Patent No. 446,583, 1,3
Triarylmethane dyes described in No. 35,422, JP-A No. 59-228.250, etc., British Patent No. 1,07
No. 5,653, ibid.

No. 153.341, No. 1,284,730, No. 1.4
75.228, merocyanine dyes described in 1,542,807, etc., U.S. Patent No. 2843.486,
Examples include cyanine dyes described in Japanese Patent No. 3,294.539 and the like.

Among these, arylidene dyes having a pyrazolone nucleus and oxonol dyes having two pyrazolone nuclei have the property of being decolorized in a developer containing sulfite, and are useful dyes as they have little negative effect on photographic emulsions. It has been used as a dye for photosensitive materials.

In particular, oxonol dyes in which the first position of the pyrazolone nucleus is substituted with an aralkyl group having a sulfonic acid group or a carboxylic acid,
It is described in JP-A-63-139949, JP-A-63-244034, and JP-A-63-264745, and is characterized in that it does not have a harmful effect on silver halide emulsions and has excellent decolorizing properties.

However, if the colored layer is a filter layer or an antihalation layer placed on the same side of the support as the photographic emulsion layer, it can maintain its effectiveness as a filter layer or an antihalation layer, and In order to avoid harmful spectral effects on other layers, it is usually necessary that those layers be selectively colored so that the other layers are not substantially colored.

However, the above-described oxonol dye in which the first position of the pyrazolone nucleus is substituted with an aralkyl group has the disadvantage of being easily diffused in order to selectively color a specific layer.

There are several methods for selectively coloring a specific hydrophilic colloid layer. The most commonly used method is to localize the dye in a specific layer by interaction with the dye molecules (considered as charge-induced attraction and hydrophobic, sexual bonding).

However, when using the mordant method, when the dyed layer and another parent wood colloid layer come into wet contact, it often happens that some of the dye diffuses from the former to the latter. Such diffusion of the dye naturally depends on the chemical structure of the mordant, but also on the chemical structure of the dye used.

In addition, when a polymeric mordant side is used, residual coloring on the photosensitive material is particularly likely to occur after photographic processing, especially photographic processing with shortened processing time, because the binding power of the mordant to the dye is This is thought to be because the dye or reversible decolorization product remains in the layer containing the mordant because some binding force still remains, although it becomes considerably weaker in an alkaline solution such as .

In addition, as another means for fixing the dye in a specific layer in a photographic light-sensitive material, JP-A-56-12639 and JP-A-55-15535
No. 0, No. 55-155351, No. 52-92716, No. 63-197943, No. 63-27838, No. 64-40827, European Patent 0015601B
No. 1, No. 0276566A1, World Patent 8 B104
It is known to have dyes present in dispersed solids, as disclosed in US Pat. However, according to our experiments, these dyes diffused into other layers, and when rapid processing was performed, dyes remained in the light-sensitive material after photographic processing, making it impossible to obtain the desired effect.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to color a hydrophilic colloid layer with a dye that is irreversibly decolored by photographic processing and does not have an adverse effect on the photographic properties of the photographic emulsion. An object of the present invention is to provide a silver halide photographic light-sensitive material.

A second object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer in which only a desired hydrophilic colloid layer is sufficiently selectively dyed with a dye, and which has excellent decolorization properties through photographic processing. That's true.

A third object of the present invention is to provide a silver halide photograph having a dyed hydrophilic colloid layer which does not adversely affect the photographic properties of the silver halide emulsion layer even with aging. The purpose of the present invention is to provide photosensitive materials.

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

(I) (Rx CH).

Q, (YtL (wherein, Rt is an alkyl group, an aryl group, a cyano group,
C0OR& , C0NRh Rt, NR6Rt, NR
t COR・, NRt Sow Rm, NR6C0NR
1Rt, C0RI Sol R1 or OR& (where R1 and R1 are each a hydrogen atom, an alkyl group, or an
), R8 represents a hydrogen atom or an alkyl group, R1 and R1 each represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group, R% represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom;

represents a benzene ring or a naphthalene ring, Y represents a free carboxylic acid group, sulfamoyl group, or sulfonamide group, LtSLm and L3 each represent a methine group, m represents 1 or 2, and n represents 0 or 1. , p represents 1, 2 represents 3, ) (n) (in the formula ・R+ ~ R: ・Q+ −Yt・Lt −Lx N
L, , m and p represent the same groups or numbers as defined in general formula (f), and q represents Oll or 2) Each substituent in the general formula will be explained in detail.

Alkyl, acyl and alkoxy groups may contain from 1 to 20 carbons, for example methyl, ethyl, isopropyl, propyl, trifluoromethyl, acetyl, benzoyl, methoxy, ethoxy, octyl, dodecyl, octadecyl, cyclohexyl, Mention may be made of t-butyl, methoxyethyl, hydroxyethyl, carboxyethyl, chloroethyl, cyanoethyl, ethoxycarbonylmethyl, methanesulfonamidoethyl.

Aryl groups can contain 6 to 20 carbons.

For example, phenyl group, naphthyl group,
It may further be substituted with other groups. The substituent is preferably a non-dissociable substituent or a dissociative substituent having a pKa (acid dissociation constant) of 4 or more in a solution with a volume ratio of water and ethanol of 1:1. For example, an alkyl substituent as described above In addition to groups, cyano, hydroxy, methoxycarbonyl, methanesulfonyl, acetylamino, N-ethylcarbamoyl,
Mention may be made of N-methylsulfamoyl, methoxy, ethoxy, acetyl, dimethylamino.

The benzene ring or naphthalene ring represented by Q is Y,
It may have a substituent other than the carboxylic acid group, sulfamoyl group, or sulfonamide group represented by, and examples of the substituent include the substituents described in the section of the aryl group above.

The methine group includes not only an unsubstituted methine group but also a substituted methine group (substituents include, for example, methyl, ethyl, benzyl, phenyl, cyano, and chlorine atoms).

) may also be included.

Halogen atoms may contain fluorine, chlorine bromine.

R, and R? or 5 or 6 formed by connecting R8 and R4
Examples of membered rings include piperidine rings, pyrrolidine rings, and morpholine rings.

A sulfamoyl or sulfonamido group may contain 1 to 20 carbons as well as a neutral group.

Examples include N-phenylsulfamoyl, N-(p-cyanophenyl)sulfamoyl, N-ethylsulfamoyl, benzenesulfonamide, and pchlorobenzenesulfonamide.

-a In formula (I) or (I[), preferred is Yl
represents a free carboxylic acid group, and m! +<1.

Specific examples of the compound represented by general formula (I) or C11) are shown below, but the present invention is not limited thereto.

Shuutt Hz CH.

・ 0OH (II-3) (II-4) (II-6) (+1-10) (II-11) (n-7) (■ 9) (■-13) (■-14) (■-15) CH.

Shi IJ (Jt1 (■-16) 17) (n-18) (I1-22) (II-24> Shiku JLJFI (II-19) H3 (n-20) No. 139949, same 6
It can be synthesized with reference to No. 4-40827, No. 59-154439, etc.

Synthesis example 1. Synthesis of (I-1) 11.6 g of 1-(4-carboxybenzyl)-3-methyl-2-pyrazolin-5-one and 7.8 g of 4-dimethylaminobenzaldehyde were mixed in 100 mj of ethanol and heated under reflux for 2 hours. . Orange crystals were collected by filtration, mixed with 100 ml of ethanol, and further heated under reflux for 1 hour.

By filtering and drying the crystals, (I-1) was converted to 16.1
I got g. λsay=465nm, g-4,9Qx
l O' (dimethylformamide) Synthesis Example 2. Synthesis of (II-14) 1-(4-carboxybenzyl)-3-methyl-2-pyrazolin-5-one 11.6 g, glutaconaldehyde cyanyl hydrochloride 7.1 g, triethylamine 17.4
Mix 50 mJ of dimethylformamide and 6 mJ of ice water.
Bottom (reaction temperature 8-10℃) 40mj of methanol was added to the 0 reaction solution stirred for 4 hours! After adding and filtering to remove dust, 36%
15 ml of salt #l was added dropwise. After stirring for 30 minutes, the precipitated black crystals were collected by filtration and washed with methanol. 11.9 g of the obtained crude crystals were mixed with 50 ml of methanol! 10 ml of triethylamine was added and dissolved. By adding 55 ml of acetic acid and stirring at room temperature, the precipitated crystals were collected by filtration, washed with methanol, and dried to obtain (II-1
11 g of 4) was obtained. λmaw 644nm, s-9,9
5X10' (Dimethylformamide) The compound of general formula (I) or (II) is used in an amount of 1 to 1000 µ per 1 d of area on the light-sensitive material, preferably 1 to 800 µ per 1 d.

-a When using a compound of formula (I1) as a filter dye or antihalation dye, any effective amount can be used, but the optical density should be in the range 0.05 to 3.5. It is preferable to use it for the purpose of coating, and it can be added at any step before coating.

The compound of general formula (I) or ([[) 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 (I) or (■) 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 in the presence of a dispersant, e.g. A method of forming by ball milling (ball mill, vibratory ball mill, planetary ball mill, etc.), sand milling, colloid milling, jet milling, roller milling, etc. [In that case, a solvent (for example, water, alcohol, etc.) may be present.] It can be formed by Alternatively, after dissolving the compound of the present invention in a suitable solvent, a poor solvent for the compound of the present invention may be added to precipitate a microcrystalline powder. In that case, a dispersing surfactant may be used. The microcrystalline particles of the compound of the invention in a dispersion may have an average particle size of The particle size is preferably 10 μm or less, more preferably 2 μm or less, particularly preferably 0.5 μm or less, and even more preferably 0.1 μm or less in some cases.

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

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

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

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

The silver halide emulsion used in the present invention has a thickness of O0j
A tabular grain emulsion in which grains having a diameter of 1 micron or less, preferably 0.3 micron or less, a diameter of 0, 1 mm or more, and an average density ratio of 1 or more occupy 104 or more of the total projected area. A monodispersed emulsion having a statistical coefficient of variation (8/d, the value obtained by dividing the standard deviation S by the diameter d in the distribution expressed by the diameter when the projected area is approximated by a circle) is -0S or less is preferable. . Further, one or more types of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsion used in the present invention is P.
, Glafkides), Chimie erPhy Photography (Chimie erPhy Photography)
sique Photographique ) (
Published by Paul Montell, /Fj7), G.F. Duffin (G, F, Duffin), Photo-gra
Phic Emulsion Chemistry)
(7 Orcal Press, 1944), by V. L. Zelikman et al., Making and Coating Photographic-Knee 1 Shore.
atingPhotographic Emulsi
on) (7 Orcal Press, 15'l Koen).

In addition, during the formation of silver halide grains, ammonia, rhodanpotash, rhodanol, thioether compounds (for example, U.S. Pat. No. 3.27/, /j7, Same No. 31!7 Hiro, No. 621, No. 3,70, No. 730,
Same day hiro, Kota 7゜hiro 32, same day gu, core tG, j
74! ), thione compounds (for example, JP-A-Shoj3-/
liμ3iy issue, same! 3-! Ko≠or issue, same! ! -77
737, etc.), amine compounds (e.g., JP-A No. 737), amine compounds (e.g., JP-A No.
No. 007/7), 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.

As a 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. Examples include 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; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl Synthetic hydrophilic polymeric substances such as single or copolymers of alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

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

Soc, Sci, Phot, Japan), 4/A
, J.

Enzyme-treated gelatin as described on page 66 may be used, and 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 I-Rhodan compound (29 μm dichloro-6-hydroxy-/,
3°! -triazine and its natochrome salts, etc.) and active vinyl compounds (/, 3-bisvinylsulfonyl-coprobanol, /, J-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether, alkyl halynylsulfonyl groups Vinyl polymers having a side chain of 2, etc.) are preferable because they quickly harden hydrophilic colloids such as gelatin and give stable photographic properties. N
-Carbamoylpyridinium salts ((/-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.)
and roamidinium salts (/-(/-chloro-/-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate, 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, merocyania dyes, complex cyanine dyes, complex melonanine dyes, holopolar-cyania dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used as basic heterocyclic nuclei/anine dyes can be applied to these dyes. That is, pylori/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, penceindolenine nucleus, indole nucleus, henzoxadole nucleus, naphthoxazole nucleus, (zotheazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc.) are applicable.These nuclei are on carbon atoms. It may have a substituent.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline as a core with a ketomethylene structure! -on nucleus, thiohydantoin nucleus, λ-thioxazolidine-co,
J-4-membered heterocyclic nuclei such as ≠-dione nucleus, thiazolidine nucleus, gugio/nucleus, rhodanine nucleus, and thiono Z-rubitur 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, amine methylbenzene compounds which are nitrogen-containing heteroartic ring nuclei groups and are substituted (for example, U.S. Pat.
3! , No. 72/), formaldehyde condensates of aromatic organic acids (e.g., US Pat. No. 3,7 μJ, 1)
10), cadmium salts, azaindene compounds, etc. US Patent No. 3,6/! ,6/
! No., same J, t/j, Buhiro/no., same! ,t/7,22!
No. 3.63! , No. 7/No. 7 is particularly useful.

The silver halide photographic emulsion used in this technology is used to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance.
Various compounds can be included. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitro(zuimidazoles, chlorobenzimidazoles, promoinzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptotetrazoles, amino Triazoles, benzotriazoles, nitrobencitriazoles, mercaptotetrazoles (especially /-phenyl-!-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriasifs; such as triazaindenes, tetraazaindenes (especially μm hydroxy-substituted (/.

3.3a, 7) Tetraazainde/s), etc.; known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonate/acid amide, etc. , many compounds can be added.

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

The light-sensitive material prepared using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for irradiation or antihalation and other various purposes.

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 one different spectral sensitivity on the support.

Multilayer natural color photographic materials usually have at least a red-sensitive emulsion layer, a green-sensitive emulsion layer and a 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, red sensitivity, green sensitivity and 1r sensitivity in this order, blue sensitivity layer, green sensitivity 1 and red sensitivity 1 in this order, or! The order is sensitivity, red sensitivity, and green sensitivity. Any emulsion layer with the same color sensitivity may be composed of two or more emulsion layers with different sensitivities to improve the achieved sensitivity,
The graininess may be further improved by using a three-layer structure.

A non-light sensitive layer may be present between one or more emulsion layers having the same color sensitivity. A configuration may also be adopted in which emulsion layers of different color sensitivity are inserted between emulsion layers of the same color sensitivity. At a high sensitivity of 4%, a reflective layer made of fine grain silver halide or the like may be provided under the high sensitivity blue sensitive layer to improve the sensitivity.

Generally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the evening-sensitive emulsion layer K (20-forming coupler), but different combinations may be used in some cases. For example, an infrared-sensitive layer may be combined to form a pseudocolor three-layer or semiconductor laser exposure layer.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl fluoride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-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.

It may be painted black for the purpose of blocking light. The formal surface of these supports is generally primed to improve adhesion to one photographic emulsion layer or the like. The entire surface of the support is coated with #1 after the primer treatment.
Glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. may also be applied.

The photographic emulsion layer and other hydrophilic colloid layers can be coated by various known coating methods such as dip coating, a-2 coating, curtain coating, and extrusion coating. As necessary, U.S. Patent No. 261/Kota Hiroshi, U.S. Pat. Co No. 1 and No. 3! .

Multiple layers may be applied simultaneously by the coating method described in No. 7, etc.

The present invention can be applied to various color and black and white photosensitive materials. Color negative film for general use or movies, color reversal film for slides or television, color positive film and color reversal film, color diffusion transfer type photosensitive materials and heat-developable color photosensitive materials. Typical examples include materials. Research Disclosure, A/7/
3 (July 1971), or by using the three-color coupler mixture described in U.S. Pat.
xa
The present invention can also be applied to black-and-white photosensitive materials such as those for use in photocopying. Backing film such as lith film or scanner film, X@, Y ilm for direct/indirect medical use or industrial use, negative black and white film for photography, black and white photographic paper, 00M or exaggerated micro film, silver salt diffusion transfer type The present invention can also be applied to photosensitive materials and printout type photosensitive materials.

When the photographic element of the present invention is applied to color diffusion transfer photography, K may be of the peel-off (beer-apart) type or of the JP-A-KOKAI No. 1-1tJzt, Equivalent No. ♂-33627, JP-A-1O-
1JOuO and British Patent/, 330. It is possible to adopt the structure of an integrated type film unit as described in Japanese Patent Application Laid-open No. 37-7/3441, which does not require peeling.

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

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

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

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phinidinediamine compounds are preferably used, and substitute examples include 3-methyl-hiro-amino-N,N-diethylaniline, 3-Methyl-Hiro-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-kuamino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-≠-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. is preferably used.

The color developer may contain 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 contains agents such as agents. Also, if necessary, preservatives such as hydroxylamine or sulfites, organic solvents such as triethanolamine, diethylene glycol,
Development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boro/hydride, adjuvants such as phenyl-3-pyrazolidone. Developers, viscosity-imparting agents, various chelating agents such as substitutes for aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphospho/acids, phosphonocarboxylic acids, West German Patent Application (OLS) No. 1, 6 Co., Ltd. The antioxidant described in No. 50 may be added to the color developing solution.

In the development process of a reversal color photosensitive material, a bleaching process is usually performed and then color development is performed. This black and white developer contains dihydroxybenzenes such as Hydroquino 7, l-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 include iron (■), cobalt (vl), and chromium (
IV), compounds of polyvalent metals such as copper CU), peracids, quinones, nitro/compounds, etc. are used. Ferricyanide as an alternative bleach; dichromate; iron(III)
or copal) (III), such as aminopolycarboxylic acids such as etele/diaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, /, 3-diamino-2-zoa-ninortetraacetic acid, or citric acid, tartaric acid. , complex salts of organic acids such as malic acid; persulfates; manganic acid groups; nitrosophenols, and the like can be used. Of these, iron ethylenediaminetetraacetate (III
) salt, diethyle/iron triaminepentaacetate Cm)* and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Additionally, the ethylenediaminetetraacetic acid iron (I[r) complex salt is particularly useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

A bleach accelerator can be used in the bleaching solution, bleach-fixing solution, and their pre-bath, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Patent No. 3. rrij, r! r, West German Patent No. 1. -ta No. 0.112, same, 03ri.

rirr issue, JP-A-33-3273 Otsu issue, same! 3-171
3/ issue, 37≠l1 issue, same! 3-Bu! 73+2, same! 3-726+23, 33-Pi630, j3
-Ta! /s3/ issue, same! 3-no op-32, same! 3-
/-Hiroshi 44th issue, same! 3-7 Hiro/Otsu-3, same j3-
2! ≠-6, Research Disclosure A/7/
Compounds having a mercapto group or a disulfide group as described in No. 7I (July 1997), etc.: '# Kaisho 60
-/Thiazolidi/derivatives as described in Koir issue;
- No., same! No. 3-32731, U.S. Patent No. 3.7ot
, thiourea derivatives described in No. zti; West German Patent No. 1,
/j7,7/! Issue, Tokukai Show 1t-/Jko3! Iodide described in the West German patent No. AJ, ≠ IO, same, 7t,
tt, polyethylene oxides described in Kou No. 30;
Polyamine compounds described in Japanese Patent Publication No. 143-1136;
Other Tokukai Akihiro Terahiro 24!3 Hiro issue, same ψter Jri AI
Aμ issue, same! 3-2 Hirotako No. 7, 54t-36727
Same issue! ! -2tjOt issue and the same! ? -7 Otsu3 Rihiro O
Compounds described in the No. 1, and iodine and bromide 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. tri3. rzr, West German patent No. 1゜+220,1
No. 12 and JP-A No. 33-23630 are preferred. Furthermore, US Patent No. Also preferred are the compounds described in H.-t3. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

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

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, fungicides and anti-piping agents that prevent the growth of various bacteria, algae, and mold. Agents, metal salts such as magnesium salts and aluminum salts, vinyl salts, surfactants for preventing drying load and unevenness, and various film hardening agents can be added as necessary. Or Photograph Inc. Science and Engineering magazine by Huenuto (L, E, West
, Phot, Sci.

A compound described in Eng., ), Volume 4, Hate-jjP, Hate-jjP, etc. may also be added. Addition of a chelating agent or anti-spill agent is particularly effective.

In the washing process, it is common to use $1 countercurrent water washing of λ class or higher to save water. Furthermore, instead of the water washing process,
-! ! A multistage countercurrent stabilization treatment step as described in Kou No. 3 may also be carried out. In the case of this step, a countercurrent column of a tank 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, the membrane p
Various buffering agents (e.g., borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid) for adjusting Ht (e.g., pH) (using combinations of acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin can be cited as examples. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (benzointhiazolinone, irithiazolone, /zimidazole, halogenated phenols, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, hardeners, and other additives may be used, and compounds for the same or different purposes may be used. Two or more types may be used in combination.

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

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

The washing and stabilization processing time of the present invention varies depending on the type of photosensitive material and processing conditions, but is usually from -0 seconds to IO minutes, preferably from 10 seconds! It's a minute.

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

For example, indoaniline compounds described in US Pat. No. 3,3 Hiroko, 3P7, US Pat. No. 3,3 Hiro-1j Tata, Research Disclosure/≠rso and US Pat. ljP
The thick base type compound described in No. 3, the Fuldol compound described in U.S. Pat. ! 4-salt complexes, urethane compounds described in JP-A-133421, JP-A-133421;
J issue, 74-11733, same! Bu-17232,
Same jj-67rltJ No. 1A-437314, No. 74-11733, No. 1t-4373, No. 74-
No. 11733, same jbuichi♂/r37, same jt7jul
lJO issue, same jt-10tJIA/ issue, same! Bu-107
Ko JΔ, J7-ta 7J37 and 37-#Jj
Various salt types of pre-kahchi described in No. tj etc. can be mentioned.

The silver halide color light-sensitive material of the present invention may optionally contain various types of 7-2 dynyl-
3-pyrazolidones may be incorporated. A typical compound is Tokkai Sho! 6-6 Hiro 33rd issue, same j7-/Hiro≠3≠7, same j7-ko///4t7, same! r-! 0j32,
tr-rot No.36, 31-30!33, j1
-jOJ3 Hiro issue, same! ? -jO! No. 33 and the same! ♂−
/1taJr issue etc.

The various processing solutions used in the present invention are used at 10 oc-to"c. The standard temperature is 336C to 31oC, but it is possible to accelerate the processing and shorten the processing time by using a higher temperature, or conversely by using a lower temperature. Improvements in image quality and stability of processing solutions can be achieved.Furthermore, in order to save silver on photosensitive materials, the method described in West German Patent No. λ, CoJt, 770 or US Pat. Treatment using cobalt intensification or hydrogen peroxide intensification may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided.

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 Ml filling amount can be reduced to half or less than the standard replenishment amount for cost reduction and the like.

When the light-sensitive material of the present invention is a color paper, it can be bleach-fixed if necessary, very generally, and even when it is a color photographic material for one-shadow use.

Next, the present invention will be specifically explained based on examples.

Example 1 (I) Preparation of tabular silver iodobromide grain emulsion In water Iz, 5 g of potassium bromide, 0.05 g of potassium iodide, 3 g of gelatin
0.0 g of thioether 110 (CHx) 5 (CHx) 5 (CHx)
33 g of an aqueous solution and an aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide were added in 45 seconds using a double jet method. Then, 2.5 g of potassium bromide was added, and then 118.33 g of nitric acid was added. An aqueous solution containing
The mixture was added over a period of 0 seconds so that the flow rate at the end of addition was twice that at the start of addition. Subsequently, 1!153.34g of nitric acid
and an aqueous solution of potassium bromide at a potential of pAg8.
The particles were grown by adding the particles over a period of 25 minutes using a controlled double jet method while maintaining the temperature at 1.

The flow rate at this time was accelerated so that the flow rate at the end of addition was eight times the flow rate at the start of addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, and then 50 cc of 1% aqueous potassium iodide solution was added over 30 seconds. After this, the temperature was lowered to 35°C, soluble salts were removed by the sedimentation method, and then the temperature was raised to 40°C, and 68 g of gelatin and 2 phenol were added.
g, add 7.5 g of trimethylolpropane, adjust pH to 6.40 with sodium hydroxide and potassium bromide, pAg
Adjusted to 8.45.

After raising the temperature to 56°C, sensitizing dye 62 with the following structure
ON and 4-hydroxy-16-methyl-1°3.3a,
160 μ of 7-chitrazaindene were added. After 10 minutes, 8.2 inches of sodium thiosulfate pentahydrate, 163 inches of potassium thiocyanate, and 5.4 inches of chloroauric acid were added, and after 5 minutes, it was rapidly cooled and solidified. In the obtained emulsion, 93% of the total projected area of all grains consists of grains with an aspect ratio of 3 or more,
The average projected area diameter for all particles with an aspect ratio of 2 or more is 0.83 μm, standard deviation 18.5%, average thickness is 0.161 μm, and the average aspect ratio is 5.16.
, the average iodine content was 0.8 mol%.

[2] Preparation of emulsion coating solution The following chemicals were added to the emulsion described in [1] per mol of halogenation to prepare a coating solution.

・2,6-bis(hydroxyamino)-4-dinithylamino-1,3.5-)riazine
80■・1.4-
Dihydroxy-3-potassium sulfate
9.3g・Sodium polyacrylate (average molecular weight 4゜10,000): 4・Og [3] Preparation of surface protective layer coating solution As the surface protective layer coating solution, an aqueous solution having the following composition per side upon drying was used. .

Gelatin 1.2g/n? Dextran 0.4g/n? Polyacrylamide 0.4g/nl Sodium polyacrylate 0.02g/n? Potassium polystyrene sulfonate 0.02g/rd Poly (methyl methacrylate/methacrylic acid; molar ratio 9:1) (particle size 4.3μ) 0.05g/rr? Dimethylsiloxane (dispersed with dodecylbenzenesulfonic acid) (particle size 0-11μ) 0.03g/rd Cetyl palmitate (dispersed with α-fudioctyl sodium salt sulfosuccinate) Particle size 0.10μ 0.03g/rd Colloidal silica 0.15g10r nitric acid IJ'F
Mu 0.06g/ITrα-Dioctyl sodium salt sulfosuccinate 0.005g/n (Dodecylbenzenesulfonic acid 0.005g/crt p-Octylphenoxyethoxyethoxyethoxyethoxyethanesulfonic acid sodium 0.005g/n1 p-Octylphenoxytriglycidyl butane Sodium sulfonate 0.005g/rrf poly(degree of polymerization 10) oxyethylene cetyl ether
0.02g/rII poly(degree of polymerization 10) oxyethylene poly(degree of polymerization 3) oxyglyceryl octylphenyl ether 0.005g/rd poly(degree of polymerization 10) oxyethylene poly(degree of polymerization)
Glyceryl cetyl ether 0.005g/rr+ Poly (degree of polymerization 10) Glyceryl dodecyl ether
0.005g/i poly (degree of polymerization 10) glyceryl p-nonylphenyl ether
0.005g//CtsuH CsF,,5OtN-4,CHzCHzO)a (C
Hz) JOJa (n#4) 0.002g/po5Ht CaP+ySOz-N-(CHiCIIxO)-, H(
n=16) 0.005g/nf 4-hydroxy-6-methyl-1,3,3a.

7-Chitrazaindene 0.03g/cd [4]
Application of undercoat layer to support A corona discharge treatment was performed on a polyethylene terephthalate film with a thickness of 175 μm that had been stretched on two wheels, and a first undercoat liquid having the following composition was applied in an amount of 5°1 ce/nl.
Apply it with a wire buff coater so that it becomes 175
After drying at ℃ for 1 minute, do the same on the opposite side.
An undercoat layer was provided.

[5] Method for producing solid fine particle dispersion of dye Compound (I-1) of the present invention was ball milled by the following method.

Zirconium oxide beads were added to a mixture of water, surfactant Triton-X-200'' and dye, the container was tightly capped and placed in a mill to grind the contents for 4 days. After dispersing in gelatin aqueous solution, it was placed on a roll mill for 10 minutes to reduce bubbles, and then the zirconium oxide beads were removed.The weight ratio of dye and gelatin was 1/1, and the amount of dye in 100 g of gelatin dispersion was 1/1.
．． It was 4g.

[6] Coating a subbing layer of a solid fine particle dispersion of a dye on a support (a coating amount of a second subbing liquid having the following composition on each of the first subbing layers on both sides described in 4) is 8°. 5cc/
A primed film was completed by coating and drying one side and both sides to form a CD.

Second undercoat liquid-4 Gelatin 10g Matting agent (polymethyl methacrylate with average particle size of 2.5 μm)
0.3gCa H9(Ci
Ha h CHCH proverb OCOCHtC4Hs (
Cg Hs )-cHcHx 0COCH5O*N
a0, 2g Solid fine particle dispersion of [5] above 12.0g (as the dye itself) Dye with the following structural formula (emulsion form) (4%) 27, 45
Add water to make 11 g.

[7] Preparation of photographic material Polyethylene terephthalate support coated with undercoat layer [6] as shown in Table 1 by co-extruding the emulsion coating solution of [2] and the surface protective layer coating solution of [3]. It was applied to both sides of the body in the same manner and dried to obtain photographic material 1-1.

In addition, photographic materials 1-2 to 1-8 were prepared by changing the solid fine particle dispersion in the second undercoating liquid to each of the compounds listed in Table 1 in photographic material 1-1.

At this time, the amount of silver coated on both sides of each material was 4゜0g/
rdC per side2. 0 g/rrr), and the amount of gelatin applied in the surface protective layer per side is 1 as shown in [3].
．． It was 2g/nl. In addition, all photographic materials are prepared by adding a hardening agent to the emulsion layer immediately before coating. It was added at a ratio of 2-bis(sulfonylacetamide/100 g-get).

(Evaluation of photographic performance) For exposure of photographic materials 1-1 to 1-8, a G-4 screen from the GRtlNEX series manufactured by Fuji Photo Film Co., Ltd. was used as a screen. According to the usual method, G
Photographic materials 1-1 to 1-8 were sandwiched between two sheets of -4 screen so as to be in close contact with each other, and exposed to X-rays through a water fan dome 10cII.

For processing after exposure, use Fuji Photo Film's RD-
The film was processed using an automatic processor, FPM-4000, manufactured by the same company, at 35° C. using Fuji F, manufactured by the same company, as a fixer.

The sensitivity was expressed as a relative sensitivity with photographic materials 1-8 set as 100.

(Measurement of Sharpness (MTF)) The MTF was measured using the combination of the 04 screen and automatic processor processing described above. Measured with an aperture of 308 m x 500 μm, and the spatial frequency is 1.

Optical density is 1 using MTF value of 0 cycles/Tsuru.

Evaluation was made in the 0 part.

(Evaluation of residual color) The residual color of the film after treatment was evaluated as follows.
The aforementioned materials were first processed in an FPM-4000 automatic processor without exposure to light. However, in order to deteriorate the conditions, an old low-pH developer was used, and the developing temperature was set at 31°C, and the washing water temperature was set at 10°C. Subsequently, the unexposed sample was processed with PPM-4000 for 90 seconds in the same manner using a normal developing solution at a developing temperature of 35°C and a washing water temperature of 25°C. For each material under the former condition, the corresponding sample under the latter condition (conditions in which no residual color occurs) was used for comparison, and the residual color was visually evaluated. As a result, there is virtually no difference in residual color (A), the former is slightly inferior (B), the former is slightly inferior but is within the acceptable range (C), the former is inferior and not acceptable ( D), and the former was ranked as very poor (E).

The results are shown in Table 1.

The present invention is based on conventional solid state dispersion methods (I-4 to I
-6), it is particularly superior in terms of residual color, and -force uniform dispersion type (I-7) has excellent residual color, but M
TF was inferior.

Table 1 Comparative compound l Compound described in JP-A-63-197943 Comparative compound 2 Comparative compound 3 Comparative compound 4 Compound described in JP-A-64-40827 JP-A-52-
Compound described in No. 92716 JP-A-63-244034
Compounds described in Example 2 After corona discharge treatment on a paper support double-sided laminated with polyethylene, a gelatin subbing layer or a dispersion of the compounds of the invention described below was applied to paper support samples A, B and C. I got it.

(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, 0.5 g of citric acid was dispersed in 25 ml of a 10% lime-treated gelatin aqueous solution, the used sand was removed using a glass filter, and the compound of the present invention n-1 was added to the sand on the glass filter. ...0.8g Compound of the present invention n-18...0.8g The attached compound was removed and 100ml of 7% gelatin solution was added. (The average particle size of the fine particles was 0.15 μm.) Paper support A Undercoat layer gelatin 0.8 g/
+d Paper support B Antihalation layer gelatin 0.6g/
n1 Compound of the present invention n-i...25
■/dCompound of the present invention ll-18...40■
/d Paper support C antihalation layer gelatin ...0.6g1
rdCompound of the present invention 11-1...4
0■/d Compound of the present invention n-18...65■
Multilayer color photographic paper samples 4-1 to 44 having the layer structure shown below were obtained on LD paper support samples A, B and C.

The coating solution was prepared as follows.

- Amount of 19.1 g of legal yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and 1.8 g of (Cpd-7)
27.2 cc of ethyl acetate and solvent (Solv-3
) and (Solv-6) were added and dissolved, and this solution was added with 10% sodium dodecylbenzenesulfonate.
It was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 3 cc. On the other hand, silver chlorobromide emulsion (bromide 1180.0 mol%
, cubic, average particle size 0.85 μ, coefficient of variation O, O
S and silver bromide go, o mol%, cubic, average grain size 0.62 μ, coefficient of variation 0.07 at 1:3.
The following blue-sensitive sensitizing dye was added to the sulfur-enhanced mixture (mixed at a ratio (Ag molar ratio)) of 5.0 per mole of ill.
A sample containing X10-' moles was prepared.

The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating solutions for layers 2 to 7 were also prepared in the same manner as the 1N coating solution. The gelatin hardening agent for each layer is l-oxy-3
,5-dichloro-S triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

1〝IL 肚1 (7゜0XIO-' mol per mole of halide w&1) Os (5゜oxto-' mol per mol of silver halide) Cs Hs I-Cs H++ (0.9X10-' per mol of Il halide) mole)
For the red-sensitive emulsion layer, the following compounds were added at 2.6 x 10-'' moles per mole of silver halide.

(4゜0 4.0 x 10-' mol per mol of il, 3. 0x10-'mol, 1.
5 mol of 0.0XlG and 8.times.10" mol and 2.times.10" of 2-methyl-5-tert-octylhydroquinone per 111 mol of halogenide, respectively, were added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-titrazaindene was added at 1.2X10-
! Mol, 1. 1×10-” moles were added.

One paper support sample A had the following comparative dyes added to its emulsion layer.

・・・・・・8■/ld ・・・・・・24■/d (The composition of each layer is shown below. The numbers represent the coating amount (g/rr). The silver halide emulsion is silver Represents the converted coating amount.

Support raw polyethylene laminate paper [4 types 12 of samples A, B, and C, in which the first layer of polyethylene contains a white pigment (TiOx) and a bluish dye (ulmarine), and an undercoat layer and an antihalation layer are provided. I” Mold 1 and the above-mentioned 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 stabilizer (Cpd-1) # (Cpd-7) Solvent (Solv-3) # (Solv-6) Second (color fixing) Gelatin 0,99 Color mixing inhibitor (Cpd-6) 0.08 Solvent (Solv-1) 0.16# (So
lv-4) 0. 08E() Silver chlorobromide emulsion (AgBr 90 mol%, cubic, average grain size 0.47μ, coefficient of variation 0.12),
AgBr 90 mol%, cubic, average particle size 0,
36μ, coefficient of variation 0.09 and the ratio l:l (A
g molar ratio)) 0.
16 gelatin 1.79 magenta coupler (ExM) 0- 32 color image stabilizer (Cpd-3) 0.20 (Cpd-
8) 0.03# (Cpd-4)
0. Ofl (Cpd-9)
0.04 solvent (Solv-2)
0.65 () Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (
Cpd-5) 0.05 Solvent (Solv-
5) 1L of 0.24 FLU chloride bromide (AgBr 10 mol%, cubic, average particle size 0.49μ, coefficient of variation 0.08) and AgB
r 70 mol%, cubic, average particle size 0.34μ
, with a coefficient of variation of 0.10, mixed at a ratio of l:2 (Ag molar ratio)) 0.23
Gelatin 1.34 Cyan coupler (ExC) 0.30 Color image stabilizer (
Cpd-6) 0.17# (Cpd
-7) 0.40 solvent (Solv-6)
0.20 = Gelatin 0.53 Ultraviolet absorber (UV-130,16 Color mixture prevention agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Kaya fukuchi LU
II Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification 17%) Liquid paraffin 1, 33 0, 17 0, 03 (Cpd-1) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixture inhibitor 1ti (Cpd-8) Color image stabilizer (Cpd-9) Color image stabilizer (Cpd-6) 2:4:4 mixture of color image stabilizers (weight ratio ) (Cpd-7) Color image stabilizer average molecular weight 80°00 (UV-6) 2:4:4 mixture of ultraviolet absorbers (M ratio) (Solv-1) Solvent (Solv-2) 2: of solvent 1 mixture (volume ratio) (Solv 5) Solvent (Solv-6) Solvent COOCm H+y (CHri- COOCa H+q Medium (Ex C) Cyan coupler (ExY) Yellow coupler (Ex M) Magenta coupler Obtained sample 2 -1 to 2-4, photosensitive needle (manufactured by Fuji Photo Film ■, FWH type, color temperature of light source 3,20
Stepwise exposures for sensitometry were provided through blue, green, and red filters using 0°K). On the other hand, the resolution (
Exposure for CTF) measurement was performed, and then the following development treatment was performed. The concentration of the obtained sample was measured and the results shown in Table 2 were obtained.

(Processing process) Support cliff ■ color development bleach fixing Wash with water drying (Processing liquid) l Nesari Shushin water diethylenetriaminepentaacetic acid Nitrilotriacetic acid I-hydroxyethylidene-1° 0g l.

800m & 0g 2° Prisoner - Plate 3 minutes 30 seconds 1 minute 30 seconds 3 minutes 1 minute i - Peel 37℃ 33℃ 24~34℃ 70~80℃ l-Diphosphonic acid (60χ solution) Benzyl alcohol Diethylene glycol Sodium sulfite Potassium bromide Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3 Monomethyl-4-aminoaniline sulfate Hydroxylamine sulfate Fluorescent brightener (WHITEX4°) Add water to pH (25°C) Ammonium thiosulfate (70%) Sodium sulfite ethylenediaminetetraacetic acid M iron 1.0m7 5m1 0m1 2, 0g 1.0g 0g 4, 5g 3.0g 1.0 1 000mj 10.25 400m1 1 50mA 8g (m) Ammonium 55g disodium ethylenediaminetetraacetate 5 Add water
1000 m 1pH (25℃)
6.70 Water permeability The following ion exchange treated tap water is deionized using an ion exchange resin to reduce calcium and magnesium to 3 ppm or less each,
Further, sodium isocyanurate dichloride zopp- was added before use. The pH of this water was 6.6.

Table 2 When the compounds according to the invention are used in an antihalation layer:
By using such an amount that the decrease in sensitivity is relatively small and residual color is not noticeable, the resolution can be significantly improved.

Rapidly developable color photographic paper (EP No. 2734) obtained by using TLC support sample and providing a high silver chloride emulsion layer thereon.
29, 273430, and Japanese Patent Application No. 63-7861), similar results were obtained.Example 3: Blue-sensitive emulsion used in Example 2 , silver bromide content 0.6
Mol% silver chlorobromide emulsion (cubic, average grain size 0.8
μ variation coefficient 0.08), green-sensitive emulsion with silver bromide content 1
．． 2 mol% silver chlorobromide emulsion (cubic, average grain size 0
．． 42μ coefficient of variation 0°07), and the red-sensitive emulsion layer was changed to a silver chlorobromide emulsion (cubic, average grain size 0°45μ coefficient of variation 0.07) with a silver bromide content of 1.5 mol%. Samples 3-1 to 3-4 corresponding to samples 2-1 to 2-4 were prepared in the same manner as in Example-2.

Each of the blue, green, and red emulsions contains the following spectral sensitizing dye and Cpd-10, and silver bromide exists in a part of the grains forming a localized phase.

11111''1 liter 1 SOs' (2゜5X10-4 mole per mole of silver halide) 0311 SOz H-N (Ct Hs)s (per mole of silver halide?, 0X10-'moJ)
0sK (halogenated! 2°SOs"5X10-' mole per mole of I) cpa-t.

(4° and 0XIO-' moles per 11 moles of I halide) (5X10-' moles per mole of silver halide in each emulsion)
The same test as in Example 2 was conducted using the obtained sensitive material using the following processing solution and processing steps.
-2 had higher sensitivity in both the red and green sensitive layers. In addition, both samples 3-3 and 3-4 had Dsin as low as that of sample 3-2, and the resolution was higher than the other samples as shown below.

Table 3 Color development, bleaching and fixing stability ■ Stable ■ 35℃ 30~36℃ 30~37℃ 30~37℃ 45 seconds 45 seconds 20 seconds 20 seconds stable ■ 30~37℃ 20 seconds stable ■
Dry for 30 seconds at 30-37℃ 70-85
°C for 60 seconds (four tanks countercurrent flow to stable Φ-Φ) The composition of each treatment solution is as follows.

Sadatachi Niri Keikasui 800m
m! Ethylenediaminetetraacetic acid 2.0g Triethanolamine 8.0g Sodium chloride 1.4g Potassium carbonate
25.0 g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g N,N-diethylhydroxylamine 4.2 g 5.6-cyhydroxybenzene 1.2.4 - Trisulfonic acid optical brightener (4,4'-diaminostilbene) Add water and H Add sodium water and add H. Sputum formalin (37%) Formalin-sulfite adduct 5-chloro-2-methyl-4- 0.3g 2.0 1 000mj! 10.10 400mt! 100mj! 8g 5g 3g 1 000mj 5.5 0, 1g 0.7g Isothiazolin-3-one 0.02g 2-Methyl-4-isothiazolin-3-one 0.01g0. O0
5 Add water to 10100O! pH4
,0 Example-4 On a subbed cellulose triacetate film support,
Sample 401, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in g/rtl of silver for silver halide and colloidal silver, and the amount expressed in g/cd for coupler additives and gelatin. The number of moles of the dye is expressed per mole of silver halide in the same layer. For chemical structural formulas that take the form of salts, the notation method used in chemical abstracts is followed.

1st layer (antihalation layer) Black colloidal silver gelatin UV~1 (R external ray absorber) UV-2 (ultraviolet absorber) UV-3 (ultraviolet absorber) Solv-2 (solvent) ExF-1 (cyan dye) ExF-2 (cyan dye) 2nd layer (low-sensitivity red-sensitive emulsion layer) Agl 4 mol% Uniform equivalent sphere diameter 0.4 μ Coefficient of variation of equivalent sphere diameter 37%, plate-like grain diameter/thickness ratio 3.0 Coated silver Amount Gelatin ExS-1 (sensitizing dye) ...4゜EXS-2 (sensitizing dye) ...0゜ExS-5 (sensitizing dye) ・
・・6゜ExS-7 (sensitizing dye) ・・6゜ExC
-1 (Cyan coupler) ExC-2 (Cyan coupler) ...Oo ...l.

...0°...0°...0°...0°...0°...0°...0.4 ...0.8 0XIO''□4 IXIO-' 5X10 -' 5 X 1 0-' ...0.17 ...0.05 ExC-3 (magenta colored cyan coupler)...
0.09 Third layer (mid-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 6 mol%, core shell ratio 2:l
Internal height Agl: equivalent sphere diameter 0.65μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grain, diameter/thickness ratio 2.0) Coated silver amount...0.55 Silver iodobromide emulsion (Ag [4 Mol%, uniform Agj type, equivalent sphere diameter 0.4, coefficient of variation of equivalent sphere diameter 37%, spherical particles, diameter/F!L ratio 3.0) Coated silver amount...0. 1 Gelatin...1,0ExS
-1 (sensitizing dye) -5,0X10-4BXS-2
(Sensitizing dye) ・0.2X10-'BxS-5 (Sensitizing dye) -8,2X10-'ExS-7 (Sensitizing dye) -8,2X10-'ExC-1 (Cyan coupler) ・0.31ExC -2 (cyan coupler) ・0.01ExC-3 (magenta colored cyan coupler)...0.09 4th N (highly sensitive green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 6 mol%, core shell ratio 2:l
internal high Agl type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 2.5) Coated silver amount...0.9 Gelatin...0.8已xS-
1 (sensitizing dye) ・6.4X10-'ExS-2
(enhancing dye) -0,9X10-'ExS5 (sensitizing dye) ・=-10,4X10-'ExS-7 (enhancing dye) -10,4X10-4ExC-1 (cyan coupler) -0,07ExC-4( Cyan coupler> ・O,0SSolv-1 (solvent)
-0,073o1v-2 (t'J agent)
・0.07Solv-3(' )
=11.02Cpct-'y (antifoggant)・
...4.6X10-'5th layer (middle layer) Gelatin ...0.6UV-
4 (ultraviolet absorber) ・0.03 [JV-5
(Ultraviolet absorber) -0,04Cpd-1 (color mixing prevention agent) ...0. 1 Polyethyl acrylate latex...0,083o1v-1 (solvent)
-0,05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion Ag+ 4 mol% uniform type 0 sphere equivalent diameter 0
．． 4μ, ball equivalent diameter 0.7μ, coefficient of variation of ball equivalent diameter 37%
, plate-like particles, diameter/thickness ratio 2, 0
Coated silver amount...0.18 gelatin
...0. 4ExS-3 (sensitizing dye) ・
2X10-'ExS-4 (sensitizing dye) ・
7XlO-'ExS-5 (sensitizing dye) ・l
Xl0-'ExM-5 (magenta coupler) ・ 0
．． 11EXM-7 (yellow colored magenta coupler) ...0.03ExY-8 (DI
R coupler) -0,013o1v-1 (solvent)
・0.09Solv-4 (i agent)
- 0.01 7th layer (medium intensity green emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, core shell ratio III
Surface height Agl type, legal equivalent type, equivalent sphere diameter 0.5 μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particle, diameter/thickness ratio 4.0
) Coated silver amount...0.27 Gelatin...0.6ExS
-3 (sensitizing dye) ・2 X I O-'Ex
S-4 (enhancing pigment) = -7X10-'ExS
-5 (sensitizing dye) -1XIO-'ExM-5
<Magenta coupler) ・0.17ExM-7 (Yellow colored magenta coupler)
...0.04ExY-8 (DIR coupler) ・
0.02Solv-1 (solvent) -0,1
4Solv-4 (t9 agent) ・0.02
8th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgT 8.7 mol%, silver amount ratio 3:4
:2 multilayer structured particles, Agl content 24 mol from inside,
0 mol%, 3 mol%, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 1.6) Coated silver amount...0.7 Gelatin...0 .8EXS-
4 (sensitizing dye) ・5.2XlO-'ExS-
5 (sensitizing dye) ・lXl0-'ExS-8
(Sensitizing dye) -0,3X10-'ExM-5 (magenta coupler)・Q, IExM-6 (yellow colored magenta coupler) ・・・0.0
3ExY-8 (DIR coupler) -0,02Ex
C-1 (Cyan coupler) -0,02Exc-
4 (Cyan coupler) ・0.013o1v-
1 (solvent) -0,253o1v-2 (solvent) ...0.06Solv-4 (solvent) ・0.01Cpd-7 (antifoggant) ... I X I O-' 9th layer (intermediate layer ) Gelatin...0.3Cpd
-1 (color mixing prevention agent) ...0.04 Polyethyl acrylate latex ...0.12 SOIV-1
(Solvent) -0,02 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Agl
6 mol%, internal high Agl type with core-shell ratio of 11, equivalent sphere diameter of 0. 7μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particles,
Diameter/thickness ratio 2.0) Coated silver amount...0.68 Silver iodobromide emulsion (Agl 4 mol%, coefficient of variation of uniform sphere equivalent diameter 37%, plate-like grains, diameter/thickness ratio 3.0) )
Coated silver amount...0.19 gelatin
...1. 0ExS-3 (sensitizing dye)
・6X10-'ExM-10 (DIR coupler)
-0,19Solv-1 (solvent) -
0,20Solv-3-0,05 11th layer (yellow filter layer) Yellow colloidal silver...0.06 Gelatin...0.8Cpd-
2 (yellow dye)...0.13Solv-1
(Solvent) 0.13Cpd-1 (color mixing prevention agent) ...0.07Cpd-6 (antifogging agent) ...0.002H-1 (hardening agent)
...0.13 12th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14.5 mol%, uniform-Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, Plate grains, diameter/thickness ratio 7°0) Coated silver amount...0.5 Silver iodobromide emulsion (Ag1 3 mol%, uniformly A
GL type, ball equivalent diameter 3.0μ, coefficient of variation of ball equivalent diameter 30%
, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount...0.
25...1. 8 ...9X10-' ...0.06 ...0.03 ...0.14 ...0.89 ...0.42 Gelatin ExS-6 (sensitizing dye) ExC-1 ( Cyan coupler) ExC-4 (Cyan coupler) ExY-9 (DIR coupler) ExY-11 (Yellow coupler) Solv-1 (Solvent) 13th layer (Intermediate layer) Gelatin...0.7ExY
-12 (DIR coupler) ・0.20Solv
-1 (solvent') ・0.34 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 10 mol%, internal high AglIM
, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver amount...0.5 Gelatin...
・0.5EXS-6 (sensitizing dye) ・lX
l0-'EXY-9 (DIR coupler) ・0.0
1ExY-11 (yellow coupler)-0,20ExC
-1 (Cyan coupler 3 -0.02SOIV-1
(Solvent) ・0.10 15th layer (first protective layer) Fine grain silver bromide emulsion (Agl 2 mol%, uniform-Agl type, equivalent sphere diameter 0.07μ) Coated silver amount...0.12 Gelatin ・・・0.9UV-
4 (ultraviolet absorber) ...0.11UV-5 (
UV absorber) ・0.16Solv-5(
Solvent) ・0.02H-1 (Hardening agent)
...0.13Cpd-5 (scavenger) ...0. 1O polyethyl acrylate latex...0.09 16th layer (second protective layer) Fine grain silver bromide emulsion (Ag1 2 mol%, uniform-Agl type,
Equivalent sphere diameter 0.07μ) Coated silver amount...0.36 Gelatin...0.55 Polymethyl methacrylate particle diameter 165μ...0. 2 H-1 (Hardening agent)...0.17 In addition to the above components, each layer contains emulsion stabilizer CPD-3 (0.17
,07g/rrr) Surfactant Cpd-4 (0.03g/rrr)
/fff) was added as a coating aid.

UV-1 CHs CHg CHg CHg olv-2 olv-4 Hz CCCHs CHl tts olv-5 UV-4 CHs +CHg　Ch+　CHg　-CHl Co OCRsCH.

x:y-70:30 (wt%) UV-5 0IV-6 CHl xF-1 xF-2 Hs　Cm”Cm　Hs ExS-3 ExS-6 ExS-7 ExS-8 tHs CHx-CHs ExS ExS-5 F, xC-2 xHS N　C! Hs xHS CH□-CH5 oi CH.

CH2 O3K H3 ExC-3 0H ExC-4 xM-7 xM-10 xM-5 H1 xY-8 xY-9 ExY-11 H-1 pd-5 CHx pd-9 (I)C@H1?0COCHI (i) Cs H+vOCOCH-So3Napd-10 Cs F+ySOs N (Cs H,)CHx C0
0Kpd-1 pd-2 pd-6 -N (Preparation of sample 402) In place of the black colloidal silver in the first layer of sample 401, compound n-14 (0.2 g/ITr) (7) ma of the present invention
A dispersion of compound 11-14 of the present invention substituted with a child dispersion was prepared in the following manner.

Water (21,1 m5) and 3 mj of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate in a 5% aqueous solution
! , 700mj of 5% aqueous solution of p-octylphenoxypoly(degree of polymerization 10) oxyethylene ether o,sg
1. of Compound 1-14 of the present invention was placed in a bot mill. oo
g and zirconium oxide beads (diameter l crane) 500mj
! was added and the contents were dispersed in a vibrating ball mill for 2 hours. The vibratory ball mill used was a BO type manufactured by Chuo Kakoki.

The contents were taken out and added to 8 g of a 12.5% aqueous gelatin solution, and the beads were filtered to obtain a gelatin dispersion of the compound of the present invention.

(Preparation of Sample 403) Sample 402 except that Compound 1-22 of the present invention was used instead of Compound H-14 of the present invention in Sample 402.
It was prepared in the same manner as .

(Preparation of sample 404) In sample 402, compound n-1 of the present invention (0.1 g/d) and n-14 were used instead of compound n-14 of the present invention.
It was produced in the same manner as sample 402 except that (0.1 g/J) was used at the same time.

(Preparation of Sample 405) In Sample 402, the following comparative compound 4-1 (compound described in JP-A-52-92716) (0.2 g/rd) was used instead of the compound of the present invention. 60
It was produced in the same manner as 2.

Comparative Compound 4-1 After exposing the samples 401 to 405 obtained as above, they were treated according to the method described in Table 4.

Table 4 Processing method Next, the composition of the treatment liquid will be described.

Matawatari Eiki (unit: g) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene-1゜l-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide■,0 Hydroxylamine sulfate 4-(N-ethyl-N-( β-Hydroxyethyl)amino]-2-Methylaniline sulfate solution was added to pH Yingyongguu 2.4 4.5 1,0 L to, os (Unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Bleach accelerator l Oo 0 100, O 1O3O o, oos mole Aqueous ammonia (27%) 15, Qal Add water to 1.0L pH 6,3 111 and 1 coat (unit: g ) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0mA! Ammonia water (27%) 6.0ml water In addition, 1.0L pH 7.2 tap water was filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through a mixed bed column to reduce the concentration of calcium and magnesium ions to 3/L or less, and then 20/L of sodium isocyanurate dichloride and 0.15 g/L of sodium sulfate were added to this solution. The pH of is 6.5-
It is in the range of 7.5.

Format (unit: g) Formalin (37%) Polyoxyethylene-p-7nononylphenyl ether (average degree of polymerization 10) Add ethylenediaminetetraacetic acid disodium salt solution to pH 2.0m A 0.3 0.05 1 , OL 5, 0-8. 0 Table 5 * Processing residual color: [Dsin (L low temperature) obtained by the processing of this example
]-(Dsln obtained by further treating with a solution of 30 g/1. of sodium sulfite for 10 minutes) The results shown in Sensitome Table 5 were obtained for the obtained sample.

By carrying out a tree and using a fine particle solid dispersion of the compound of the present invention in an antihalation layer, it is possible to obtain a color photographic light-sensitive material which is free of sensitivity loss, fogging, and residual color after processing and has a small amount of residual silver.

Example 5 (Preparation of Sample 501) A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm, and designated as Sample 50I. The numbers represent the amount added per d.

1st layer: antihalation layer black colloidal silver 0.25g gelatin 1.9gU-10.04g U-20.1g U-30.1g 0i1-10.1g 2nd layer: intermediate layer gelatin 0.40gCpd-
D 10 ■0il-34
0■ Third layer: Fine grain silver iodobromide emulsion (average grain size 0.06μ, Agl content 1 mol%) covered with an intermediate layer tBIo
, 05g gelatin 0.4g 4th layer:
Iodobromide [Jl
(Average particle size Q, 4p, monodisperse cubic with Ag+ content of 14°5 mol% and average particle size of 0.3μ, Agl content 4.5 mol%
Monodispersed cubic 1:1 P mixture) Silver amount 0.4 g Gelatin 0.8 g Coupler C-10,20 g Coupler C-90,05 g 01l-10,1 cc 5th layer: Medium red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (monodisperse cubic with average grain size 0.5μ and Agl content 4 mol%) Silver amount 0.4 g Gelatin 0.8 g Coupler C-10,2g Coupler C-20,05g Coupler C-30,2g 0f11 0.1cc
6th layer: High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally enhanced with sensitizing dyes S-1 and S-2 (monodisperse twinned grains with average grain size 0.7μ and Agl content 2 mol%) 8 10.4 g 1.1 g 0.7 g Coupler C-10.3 g 7th layer: Intermediate layer gelatin 0.6 g Dye D-
10.02g 8th layer: Silver iodobromide emulsion covered with intermediate layer (average grain size 0.06μ, Agl
Content 0.3 mol%) Gelatin 1.0gCpd-A
0.2 g 9th layer: Low-speed green-sensitive emulsion layer Gelatin coupler C-3 Silver iodobromide emulsion spectrally enhanced with sensitizing dyes S-3 and s-4 (average grain size 0.4 μ, Agl content 45 mol) % monodisperse cubes and 1:l mixture of monodisperse cubes with average particle size 0.2 μ and Agl content 14.5 mol %) Silver amount 0.5 g Gelatin 0.5 g
Coupler C-40, 10g Coupler C-70, 10g Coupler C-80, lOg Cpd-B O, 03gCpd
-E O,1gCpd-F
O,1gcpd-c
O, 1g Cpd-HO, 1g 10th layer: Low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and s-4 (average grain size 0.5μ, Agl content 3 mol% (monodisperse cube) Silver amount 0.4g Gelatin 0.6g Coupler C
-40,1g Coupler C-70,1g Coupler C-80,1g Cpd-B O,03
gCpd-E O,1
gCpd-FO・
Igcpa-c'o
, 05g Cpd-HO, 05g 11th layer: Medium-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size in terms of spheres 0.6μ, Agl content 0) .6μ, monodispersed flat plate with an average diameter/thickness of 7) Amount of silver 0.5 g Gelatin 1.
0g Coupler C-40,4g Coupler C-70,2g Coupler C-80,2g Cpd-B O,08gCpd
-E O,1gCpd-F
O, 1g cpd-cO, ]g Cpd-HO, 1g 12th layer: Intermediate layer gelatin 0.6g Dye D-2
0.05g 13th layer: Yellow filter layer Yellow colloid! I Silver amount 0.1g Gelatin 1.1gCpd-A
O, 01g 14th layer: Intermediate layer gelatin 0.6g 15th layer:
Silver iodobromide emulsion (low-speed blue-sensitive emulsion layer) sensitized with enhancing dyes S-5 and S-6 (
Average particle size 0. (1:1 mixture of monodisperse cubes containing 4μ, 13 mol% Ag+ and monodisperse cubes having an average particle size of 0.2μ and 3 mol% Agl) 1mlto
, 6g Gelatin 0.8g Coupler C-50, 6g 16th layer: Medium-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Silver II 0.4g gelatin
0.9g Coupler C-50, 3g Coupler C-60, 3g 17th layer: Highly sensitive blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-S and S-6 (
Average particle diameter when converted to spheres: 0.7 μ, Agl content: 1.5 mol%,
Tabular grains with an average diameter/thickness of 7) Silver content: 0.4g Gelatin: 1.2g
Coupler C-60.7g 18th layer: 1st protective layer gelatin 0.7 gU-10
,04g U-30,03g U-40,03g U-50,05g U-60,05g pac-c Dye D-3 19th layer: Fine grain silver iodobromide emulsion covered with second protective Xi layer 06μ, Agl If mol%) t! INt 5g (Average particle size O1 0,1 Gelatin 20th layer: Third protective layer Gelatin 0.4g Polymethyl methacrylate (Average particle size 1.5μ) 0.1g 4:6 copolymer of methyl methacrylate and acrylic acid Combined (average particle size 1.5μ) 0.1g silicone oil
0.03 g Surfactant W-13.0 0.4 In addition to the above composition, gelatin hardener H-1 and a coating and emulsifying surfactant were added to each layer.

-1 H H -6 7 Kabra-C-8 -9 11-1 Dibutyl phthalate 11-2 Tricresyl phosphate-6 S ■ -7 (CHI)45o3s C,H -1 CHz =C)lsOt CHz C0NHCHzcu
t-CHSOYCH,C0NHCHffiHs (Preparation of sample 502) In sample #J501, the yellow colloidal silver of the 13th layer was
Compound of the present invention! -6 (0.2 g/rd) fine particle dispersion. The fine particle dispersion (1)-6 was prepared in the same manner as the fine particle dispersion (14) in sample 402 in Example 4.

(Preparation of sample 503) In sample 502,! Sample 502 was prepared in the same manner as Sample 502 except that Compound 1-16 of the present invention was used instead of -6.

(Preparation of sample 504) Sample 502 was prepared in the same manner as sample 502, except that compound 1-17 of the present invention was used instead of I-6.

After exposing the samples 501 to 504 obtained as above, they were processed in the following manner.

Process time Temperature first development 6 minutes 38℃ water washing 2 minutes inversion 2 minutes 38℃ color development 6 minutes adjustment 2 minutes bleaching 6 minutes fixing 4 minutes water washing 4 minutes stabilizing 1 minute room temperature The composition of the drying solution used is as follows.

Seirinen Kisui 700m
ff1 Nitrilo-N,N,N-)limethylenephosphonic acid pentatrirum salt 2g Sodium sulfite 20g Hydroquinone monosulfonate
30g sodium carbonate (-water salt)
30g 1-phenyl-4methyl-4 hydroxymethyl-3 and lazolidone Potassium bromide Potassium thiocyanate Potassium iodide (0.1% solution) Add water and invert Kisui nitrilo-N,N,N-)rimethylenephosphonic acid・Pentatrirum salt Stannous chloride (trihydrate) p-Aminephenol Sodium hydroxide Add glacial acetic acid water to make nitrilo-N,N,N-trimethylenephosphonic acid pentatrirum salt 2, 5g 1, 2g 2m7! 000m1 7 00m1 g g O,1g g 5m1 1 000m1 7 Q 0mff1 g Sodium sulfite 7g Sodium triphosphate (I2 hydrate) 36g Potassium bromide 1g Potassium iodide (0,
1% solution) 90mi! Sodium hydroxide
3g citradinic acid
1.5g N-ethyl-N-(β-methanesulfonamidoethyl)-3 methyl-4-aminoaniline sulfate 11g3.6~
Add 1 g of dithiaoctane-1,8-diol to 1000 ml! Bamboo water 700
m1 Sodium sulfite 12g Sodium ethylenediaminetetraacetate (trihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid
Add 3 ml of water and add 1 ml of sodium ethylenediaminetetraacetate (trihydrate) Iron(III) ethylenediaminetetraacetate Ammonium (trihydrate) Potassium bromide Add 1 ml of water and add 1 ml of water Sodium 1,000 osulfate Sodium sulfite Sodium bisulfite Sodium water is added to add water to formalin (37% by weight) Fuji Drywell (surfactant made by Fuji Film ■) 000mJ 800mm! g 20g 00g 1000mj! 800ml 80.0g 5, Og 5,0g 000mj 800 mj 5.0m7 5, 0mj Water was added and 1000ml of the obtained sample was subjected to sensitometry, and the results shown in Table 6 were obtained. However, in the 6th Jw, the value of the amount of residual silver is the result of processing with the bleaching time shortened to 2 minutes.

Dm after subsequent exposure When the compound of the present invention is used as a yellow filter, a color photographic light-sensitive material with less decrease in sensitivity of the blue-sensitive layer than yellow colloidal silver and a small amount of residual silver can be obtained. It is also seen that since there is no capri in the blue-sensitive layer based on yellow colloidal silver, a color photographic material with a high Dm can be obtained.

Example 6 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic optical material was prepared by coating the next four layers from the next layer on the front side of 0 micron) and the five layers to the sixth layer on the back side. The polyethylene on the coating side of the first layer contains titanium oxide as a white pigment and a trace amount of ultramarine as a bluish dye (the chromaticity of the surface of the support is L", a*, b
The values were 88.0, -0.20, and -0.75 for the s system. )
.

(Photosensitive layer composition) The components and coating amount (g/rd unit) are shown below. For silver halide, the coating amount is shown in terms of silver.

The emulsion used in each layer was prepared according to the manufacturing method of emulsion EMI. However, a Lippmann emulsion with no surface chemical sensitization was used for the Deshi four-layer emulsion.

1st layer (antihalation layer) Black colloidal silver...0.10 Gelatin...0.70 2nd layer (
Intermediate layer) Gelatin...0.70 3rd
Layer (low sensitivity red sensitivity N) Silver bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (average grain size 0.25 μ, size distribution [coefficient of variation] 8%, octahedral) ...0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) (silver chloride 5 mol%, average particle size 0.40μ
, size distribution 10%, octahedron)
...0.08 gelatin...
・1.00 cyan coupler (ExC-1, 2, 3:
1:0.2)...0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalent)...0.1
8 Anti-stin agent (Cpd-5)...0.003
Power puller dispersion medium (Cpd-6)...0.03 Coupler solvent (Solv-1, 2, 3, etc....0.12 4th layer (high sensitivity red sensitive layer) Red sensitizing dye (ExS- Silver bromide (average grain size 0.60μ, size distribution 15%) spectrally sensitized with
, octahedron) ...0.14 gelatin
...1.00 cyan coupler (ExC-1
, 2, 3 to 1:l:0.2) ・
...0.30 Antifading agent (Cpd-1, 2, 3, 4 equivalent) ...0.18 Coupler dispersion medium (Cpd-6) ...0.03 Coupler solvent (Solv-1, 2, 3 equivalents)...0.1
2 5th layer (intermediate layer) Gelatin...1.00 Color mixing prevention agent (Cpd-7)...0.08 Color mixing prevention agent solvent (Solv-4, 5 equivalent)...0.16 Polymer latex (Cpd-8)...0. lO 6th
Layer (low sensitivity green sensitive layer) Bromide 11 spectrally sensitized with green sensitizing dye (ExS-4)
(Average particle size 0.25μ, size distribution 8%, octahedron) ...0.04 green sensitizing dye (ExS-
Silver chlorobromide (silver chloride 5 mol%, average grain size 0.40μ, size distribution 1O%, octahedral) spectrally sensitized by 4)
...0.06 Gelatin ...0.80 Mazenk Kabler (ExM-1, 2, 3 equivalent) ...0.1
1 Anti-fading agent (equal amounts of Cpd-9, 26)...0.15 Anti-staining agent (Cpd-IQ, 11.12.13 in 1 amount)
0 near:7:1 ratio)...0.025 force puller dispersion medium (Cpd-6)...0.05 coupler solvent (
Solv-4, 6 equivalent)...0.15 7th layer (highly sensitive green-sensitive layer) Silver bromide (
Average particle size 0.65μ, size distribution 16%, octahedral)...0. IO gelatin
...0.80 magenta coupler (E3CM-
1, 2, 3 equivalents) ... 0.11 Anti-fading agent (Cpd-9, 26 equivalents) ... 0.15 Anti-staining agent (Cpd-10, LL, 12.13 equivalent)
0 near:7:1 ratio)...0.025 force puller dispersion medium (Cpd-6)...0.05 coupler solvent (
Solv-4, 6 equivalent)...0.15 8th layer (intermediate layer) 9th layer (yellow filter layer) same as the 5th layer Yellow colloidal silver gelatin Color mixing prevention agent (Cpd-7) Color mixing prevention agent solvent (Solv-4, polymer latex 10th layer (intermediate layer) same as 5th layer...0.12...0.07...0.03 5 equivalents)...0. lO...0.07 (Cpd-8) 1st I layer (low sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.40μ Size distribution 8%, octahedral) ...0.07 blue sensitizing dye (ExS-
5,6) spectrally sensitized with chlorobromide $1 (1.8 mol% chloride, average particle size 0.60 μ, size distribution 11%, octahedral)...0.14 Gelatin...0. 80 yellow coupler (BxY-1,2 etc...0.35 Anti-fading agent (Cpd-14) - 0.1O Anti-stinting agent (Cpd-5,15 in 1j5 ratio)
...0. OO7 force puller dispersion medium (Cpd-6)...0.05 coupler solvent (
Sol v-2) -0,10 12th layer (high sensitivity blue-sensitive layer) Im bromide (average particle size 0.85μ, Size distribution 1
8%, octahedral) ...0.15 gelatin yellow coupler ...0.60 2 equivalents) ...0.30 ...0.10 1:5 ratio of 15 ...0.0 < 17 ...0.05 ...0.10 (ExY-1゜antifading agent (Cpd-14) anti-stinting agent (Cpd-5, in) coupler dispersion medium (Cpd-6) coupler solvent (3o1v 2) 13th layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (Cpd-2, ...1.00 4.16 equivalent) ...O, SO Color mixing prevention agent (Cpd-7, 17 equivalent) ... 0.03 Dispersion medium (Cpd-6)...0.02 Ultraviolet absorber solvent (Solv-'l, 7 equivalents)...0.
08 Anti-irradiation dye (Cpd-13, 19, 20
(10=13:20 ratio)...O,OS 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1
μ)...0.03 Acrylic modified copolymer of polyvinyl alcohol...0.01 Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
...0.05 gelatin
...1.80 gelatin hardening agent (H-1, H-
2nd grade...0.18 15th layer (back layer) Gelatin...2.50 Ultraviolet absorber (Cpd-2, 4, 16 etc....0.50 16th layer (I1 side protective layer) ) Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
...0.05 gelatin
...2.00 Gelatin hardening agent (H-1, H-
2 equivalents)...0.14 How to make emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 75°C over 15 minutes with vigorous stirring.
Octahedral bromide root particles with an average particle size of 0.40μ were obtained. To this emulsion was added 0.3 g of 3.4-dimethyl-1 per mole of silver.
, 3-thiazoline-2-thione, 6* sodium thiosulfate and 7* chloroauric acid (tetrahydrate) were added in sequence at 75°C.
Chemical sensitization treatment was performed by heating for 0 minutes. Using the thus obtained grains as cores, they were further grown in the same precipitation environment as the first time, and finally an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0°7μ was obtained. The coefficient of variation was approximately 10%.

To this emulsion were added 1.5 μ of sodium thiosulfate and 1.5 μ of chloroauric acid (tetrahydrate) per mole of silver, and the
Chemical sensitization was carried out by heating for a minute to obtain an internal latent image type silver halide emulsion.

Each photosensitive layer contains ExZK-1 and ExZK- as nucleating agents.
Cpd-22 was used as a nucleation accelerator in an amount of 10-'10-'' weight percent based on the silver halide, and Cpd-22 was used as a nucleation accelerator in an amount of 10-'' weight percent. Furthermore, each layer contains alkanol X as an emulsification and dispersion aid.
C (Dupon) and sodium alkylbenzenesulfonate, succinate ester and M as coating aids.
agefacF-120 (manufactured by Dainippon Ink Co., Ltd.) was used. (cpa 23.24.25) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as sample-601.

In Sample 601, the ninth layer of yellow colloidal silver was replaced with Compound 1-6 of the present invention prepared in the same manner as in Example 5 (
0.2g/n? ) was replaced with the fine particle dispersion, and was used as sample hole 602.

A sample obtained by replacing compound 1-6 with 1-16 in sample 602 was designated as sample Na603.

Compound in sample 602! A sample in which -6 was replaced with 1-17 was designated as sample magnet 604.

The compounds used in the examples are shown below.

ExS ■ tHs ExS-2 t Hs (CHz)3 (cHt)s O3- 03H ExS-3 xHs O1Na Oi pd-4 ExS zHs 503 H-N CCx Hs)x pd-1 pd-2 pd-12 pd-13 pd 15 pd-16 pd-18 pd-25 H pd-17 pd-26 pd-19 pd-20 pd-22 pd-23 xM-1 xM-3 pd 4 Hs ExY-1 ExY-2 Solv-I Solv- '1 o1v-3 Solv~4 Solv-5 Solv-6 (2-ethylhexyl) sebacate trinonyl phosphate (3-methylhexyl) phthalate tricresyl phosphate butyl phthalate trioctyl phosphate Solv-7 -1 -2 ExZK 1 ExZK-2 Di(2-ethylhexyl)phthalate 1.2-bis(vinylsulfonylacetamido)ethane 4.6-dichloro-2-hydroxy-1,3,5-)riazine Na salt 7-(3-ethoxythio carbonylaminobenzamide)-9-methyl-IO-prohagilu 1. 2. 3.
4-Tetrahydroacridinium trifluoromethanesulfonate 2- (4-(3-(3-(3-(5-(3-(2-chloro-5-(l-dodecyloxycarbonylethoxycarbonyl)phenylcarbamoyl2-4 -Hydroxy-
1-naphthylthio)tetrazol-1-yl]phenyl)ureido]benzenesulfonamide I phenyl]-1
- Formylhydrazine After imagewise exposing the silver halide color photographic materials 601 to 604 prepared as described above, the cumulative replenishment amount of the solution is adjusted to the tank capacity using the method described below using an automatic processor. Continuous treatment was carried out until the amount increased 3 times.

Tank color development 135 seconds 38℃ 15j bleach fixing
40# 33a 3# water washing (ll 40#
33# 3#Wash +21 40# 3
3# 3"30#80〃 300gtj/-" 00 20 l The method of replenishing the washing water is to replenish the washing water to the washing bath (2),
A so-called counter-current replenishment method was used in which the overflow solution from step 2) was led to the washing bath (I1).At this time, the amount of bleach-fixing solution brought into the washing bath (I) from the bleach-fixing bath for photosensitive materials was 3.
5mj! /af, and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in was 9.1 times.

The composition of each treatment liquid was as follows.

D-Sorbit Naphthalenesulfonic acid Natrirum formalin condensate Ethylene diamine Tetrakis methylene phosphonic acid Diethylene glycol Benzyl alcohol Potassium bromide Benzotriazole Sodium sulfite N,N-bis(carboxymethyl)hydrazine D-Glucose triethanolamine N-Ethyl-N-(β -methanesulfonamidoethyl) = 3-methyl-4-amino 0.15 g 0.15 g 1.5 g 12, □ej! 13.5ap1 0.80g 0.003g 2.4g 6.0g 2.0g 6.0g 6.4 g 0.20g 0.20g 1.58 16.0m11 18, (IwJ 0.004g 3.2g 8.0 g 2.4g 8.0 g 8.58 Aniline sulfate Potassium carbonate 30.0g Optical brightener (diaminostil 1.0g pen type) Add to make it 1ooo! pH (25℃) 10.2525.0 g 1 .2 g 1000 Oka 1 10.75 Ethylenediamine tetraacetic acid, di-sodium, dihydrate Ethylenediamine tetraacetic acid, Fe(III), ammonium, dihydrate, ammonium thiosulfate (700 g/j) p-) Sodium luenesulfinate Sodium bisulfite 5-Mercapto-1,3,4 triazole 4.0g 10.0g 80m 1 20.0g 20.0g 0.5g Same ammonium nitrate as mother liquor 10.0g pH (25℃) 6.20 Water description 2 Mother liquor, replenisher Tomo tap water was passed through a mixed bed column filled with a strong acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH anion exchange resin (Amberlite IR-400). Then, sodium dichloride isocyanurate 20/1 and sodium sulfate 1.5 g/l were added.The pH of this solution was 6.5.
It was in the range of ~7°5.

On the other hand, before exposing samples 601 to 604 imagewise,
After being left at 55% RH for 3 days, the same treatment was carried out by imagewise exposure.

The results are shown in Table 7.

Table 7 July 37, 1999 It can be seen that when the compounds of the present invention are used, color photographic materials with little change in Ds+in over time can be obtained.

1゜ 2゜ 3゜ Display of incidents name of invention person who makes corrections Relationship with the incident Heisei Special application number iti, ztri Silver halide photographic material

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a hydrophilic colloid layer containing a solid fine particle dispersion of a compound represented by the following general formula (I) or (II). (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is an alkyl group, an aryl group, a cyano group,
COOR_6, CONR_4R_7, NR_6R_7,
NR_7COR_8, NR_7SO_2R_8, NR_
6CONR_6R_7, COR_5SO_2R_8 or OR_6 (where R_6 and R_7 are each a hydrogen atom,
It represents an alkyl group or an aryl group, R_5 represents an alkyl group or an aryl group, and R_4 and R_7 may be connected to form a 5- or 6-membered ring. ), R_
2 represents a hydrogen atom or an alkyl group, R_3 and R_
4 each represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and R_3 and R_4 may be connected to form a 5- or 6-membered ring. R_5 is a hydrogen atom, an alkyl group,
represents an alkoxy group or a halogen atom, Q_1 represents a benzene ring or naphthalene ring, Y_1 represents a free carboxylic acid group, sulfamoyl group or sulfonamide group, L_1, L_2 and L_3 each represent a methine group, m is 1 or 2, n represents 0 or 1, p
represents 1, 2 or 3. ) (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, Q_1, Y_1, L_1, L
_2, L_3, m and p represent groups or numbers as defined in general formula (I), and q represents 0, 1 or 2. )