JPH0313937A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To dye only the desired layer to absorb light in a near IR region and to speed up the decoloration by a photographic processing by incorporating the solid fine particle dispersing element of a specific dye into the photosensitive material. CONSTITUTION:This photosensitive material is provided with the hydrophilic colloidal layer contg. the solid fine particle dispersing element of the dye expressed by formula I. In the formula, R1, R2 denote alkyl, alkenyl, etc.; R3, R4 denote H, monovalent group; Z1, Z2 denote the atom group necessary for forming a desired nitrogenous heterocycle; L is methyne, a combination group combined with a methyne group by conjugated double bonds; X<-> denotes anion; l1, l2 denote 0, 1. This dye (e.g.: the compd. expressed by formula II) is ground to fine particles by a sand mill, etc. and can be dispersed into an aq. gelatin soln. The incorporation of these particles into a halation preventive layer, etc., is possible.

Description

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

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

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

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

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

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

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

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

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

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

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

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

For example, US Pat. No. 2,548,564 discloses a method in which a hydrophilic polymer having an opposite charge to a dissociated anionic dye is made to coexist in a layer as a mordant, and the dye is localized in a specific layer by interaction with dye molecules. , 4,124,38
No. 6, No. 3,625.694, etc.

In addition, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in JP-A-56-12639 and JP-A-55-1553.
No. 50, No. 55-155351, No. 63-27838
No. 63-197943, European Patent No. 15,601
No. 274,723, No. 276.566, No. 29
No. 9,435, US Pat. No. 4,803,150, International Application Publication (WO) No. 88104794, and the like.

In addition, a method of dyeing a specific layer using metal salt fine particles to which a dye has been adsorbed is disclosed in U.S. Patent No. 2,719,088;
No. 496,841, No. 2,496゜843, JP-A-6
No. 0-45237 and the like.

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

On the other hand, dyes in the form of solid fine particle dispersions that can be used in photographic materials sensitive to near-infrared light, which absorb light in the range of 700 μm to 11009p, and which are sufficiently decolorized or washed out during development processing, are also available. There was a need for a hydrophilic colloid layer containing the following, but a dye suitable for this application had not been found.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to provide a photographic light-sensitive material containing a dye in the form of solid fine particle dispersion designed to dye a specific hydrophilic colloid layer in the photographic light-sensitive material and to rapidly decolorize it during the development process. The goal is to provide the following.

Another object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a dye in which solid fine particles are dispersed so as to absorb light in the near-infrared region and rapidly decolorize during development. It is to provide.

[Means to solve the problem]

An object of the present invention is to provide a hydrophilic colloid layer containing a solid fine particle dispersion of a dye represented by the following general formula (I). The present invention has been completed based on the discovery that the above problem can be solved by a silver halide photographic light-sensitive material.

General formula (1) In the formula, R+ and Rz each represent an alkyl group, an alkenyl group, or an aryl group, and R3 and Ra each represent a hydrogen atom or 1
Represents a valence group; 2. ．． 2. each represents a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocycle, and L
represents a methine group or a linking group formed by connecting 3.5 or 7 methine groups via a conjugated double bond, X- represents an anion, and 1. ．． 1. each represents 0 or 1.

- In Shipman (1), R,, R, may further have a substituent. Preferred among the substituents of these groups are those in which the hydrophobicity parameter, π, proposed by C. Hansch et al. is in the range of -3.5 to 15. Note that the hydrophobicity parameter can be calculated according to the following literature.

1) C9transch et al., J. Med, Chem.
, vol. 16, p. 1207 (published in 1973), 2) C0 Hansch et al., same magazine, vol. 20, 304
Page (published in 1977) Preferred groups represented by R1 or R are:
A substituted or unsubstituted phenyl group, a substituted or unsubstituted lower alkyl group (having 1 to 8 carbon atoms), or a substituted or unsubstituted lower alkenyl group (having 2 to 8 carbon atoms). When R or R2 has a substituent, particularly preferred substituents include a carboxylic acid group, a hydroxy group, a benzenesulfonamide group, a cyano group, a halogen atom (F, Cf, Br, I), and substituted or unsubstituted phenyl. groups (e.g. phenyl, p-carboxyphenyl, p-hydroxyphenyl, m-carboxyphenyl,
0-carboxyphenyl, p-methanesulfonamidophenyl, m-chlorophenyl, p-methylphenyl, etc.)
, alkylthio groups (e.g. methylthio, butylthio, etc.), substituted or unsubstituted phenylthio groups (e.g. phenylthio, p-hydroxyphenylthio, m-carboxyphenylthio, 0-carboxyphenylthio, p-chlorophenylthio, m-methylphenylthio) etc.).

Among the groups represented by R3 or R, particularly preferred are unsubstituted alkyl groups having 2 to 8 carbon atoms or unsubstituted alkenyl groups having 2 to 8 carbon atoms, among which those in which R1 and R7 are the same is most preferred.

The monovalent group represented by R,, R4 has 1 to 1 carbon atoms.
8 alkyl groups (e.g. methyl, ethyl, t-butyl), alkoxy groups having 1 to 8 carbon atoms (e.g. methoxy,
ethoxy, phenethyloxy, butoxy, octoxy,
carboxyethoxy), phenoxy group (e.g., unsubstituted phenoxy, p-chlorophenoxy), aryl group (
For example, phenyl, naphthyl), cyano group, halogen atom (e.g. F, Cl5Br, I), carboxylic acid group, hydroxy group, sulfonamide group (e.g. methanesulfonamide, benzenesulfonamide), sulfamoyl group (e.g. Substituted sulfamoyl, methylsulfamoyl, ethylsulfamoyl, phenylsulfamoyl, etc. are preferred.

The 5- or 6-membered nitrogen-containing heterocycle represented by L or Zz may be a fused ring, such as an oxazole ring, a benzoxazole ring, an isoxazole ring, a naphthoxazole ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, or an indolenine ring. ring, imidazole ring, benzimidazole ring, naphthoimidazole ring, quinoline ring, pyridine ring, and the like.

The linking group represented by L represents a substituted or unsubstituted methine group, or a linking group formed by linking 3.5 or 7 substituted or unsubstituted methine groups via a conjugated double bond. Preferably, it is represented by a person (al or j).

-Sailor (a) -C= -Monka (b) General formula ((to) -CH=CH-C=CH-CH= General formula (C) General formula (d) General formula (e) General formula (f) CH=C-CH-CH-CH= General formula (5) %formula% ) General formula (j) ,”-Z’i’.

-i In formula (a) to j), Y represents a hydrogen atom or a monovalent group. In this case, the monovalent group includes a lower alkyl group such as a methyl group, a substituted or unsubstituted phenyl group, and a benzyl group. aralkyl groups such as groups, lower alkoxy groups such as methoxy groups, dimethylamino groups, diphenylamino groups, methylphenylamino groups, morpholino groups,
Imidazolidino group, disubstituted amino group such as ethoxycarbonylpiperazino group, alkylcarbonyloxy group such as acetoxy group, alkylthio group such as methylthio group,
Cyano group, nitro group, F, CF! , halogen atoms such as Br, etc. are preferable.

- In the pattern hole (j), Z represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring, and a cyclopentene ring,
Examples include a cyclohexene ring and a 4,4-dimethylcyclohexene ring.

The anion represented by X- is a monovalent or divalent ion that supplies the number of negative charges necessary to neutralize the charge of the cation moiety.

Examples of anions represented by X- include C2B1, I
Halogen ions such as -, SO4"-H3O4-, CH
7ztz-t-/lz sulfate ions such as sO3Oi-,
Sulfonate ions such as paratoluenesulfonate ion, naphthalene-15-disulfonate ion, methanesulfonate ion, trifluoromethanesulfonate ion, octanesulfonate ion, acetate ion, p-chlorobenzoate ion, trifluoroacetate ion, Carboxylic acid ions such as oxalate ions and succinate ions, PFb”
Examples include heteropolyacid ions such as BF, -, ClO4-, IO, -tungstate ion and tungstophosphate ion, and phenolate ions such as L'po4-, NO3- and picrate ion.

Preferred anions represented by X- are C1
-, B r-, I-, C[(sO3Os-CtHsO3
03-, perfluorosulfonate ions such as paratoluenesulfonate ion, p-chlorobenzenesulfonate ion, methanesulfonate ion, butanesulfonate ion, naphthalene-1,5-disulfonate ion, trifluoromethanesulfonate ion, PFb -,BF,-
, (10,-, etc., and particularly preferred ones are trifluoromethanesulfonate ion, PFth-, Cff1
Among them, trifluoromethanesulfonic acid ion and PF6- are most preferable since there is no risk of explosion.

Any substituents possessed by the compound represented by the general formula (I) are preferably groups having a pKa (acid dissociation constant) of 2 or less, such as sulfonic acid groups, and preferably groups having a pKa of 3 or more. In particular, it is preferable to have one to four groups having a pKa of 3 or more and 12 or less, particularly preferably 4 or more and 11 or less, in order to prevent the outflow from the photosensitive material during development. Examples of this birch group include carboxyl group, phenolic hydroxyl group, -N HSO - group, -cocLCO-
and active methylene groups such as.

Particularly preferred in general (I) are those in which Z and Zz each represent a quinoline ring, a benzoxazole ring, an isoxazole ring, a benzimidazole ring, or a benzothiazole ring, and L forms a di- or tricarbocyanine dye. The dye molecule contains at least two groups selected from the group consisting of a carboxylic acid group, a sulfonamide group, a sulfamoyl group, or a phenolic hydroxyl group.

Specific examples of the compound represented by the general formula (1) used in the present invention are listed below, but the scope of the present invention is not limited only to these.

-1 -2 -3 -4 ! -8 -9 ! -10 -7 CHl CHl -11 ■ 12 CJ4CO1)H -13 CIl5 Js C, H, C00)1 CIH4C00H CJ4COOH ■-15 C,H.

(CL)zcOOH CHICOOH ■ 0 zHs Js CIHS −16 CIl, C0OH tHs ■-17 Js C.HS -18 ■ Js Js ■ 9 cuzcooH CI(ZCOOH ■-23 -24 CIHS C2H.

■-25 CIHS The dye of the present invention with the general formula (N) can be synthesized using the following synthesis examples, JP-A No. 46-14830, JP-A No. 52-10-727, JP-A No. 62-123454, F.M. Balmer ( ``The Cyanine Guise and Related Compounds'' by F. M. Haller) (
'The cyanine dies and rel
ated compounds”) Inter Science Publishers (Inter-5science P
Heterocyclic Compounds Special Topics in Heterocyclic Chemistry (1964) and D.M. Sturmar (1964).
erocyclic compounds-5pec
ial topics in heterocycle
c chemistry -) can be synthesized according to the method described in John Wiley & Sons, Inc. (1977).

Synthesis Example 1 (Synthesis of r-'13) After the reaction was completed, the reaction solution was cooled to room temperature, and then ethyl acetate 50-
was added, coarse crystals were precipitated. The crude crystals were dissolved in 300 methanol and further dissolved in NaPF.

1.7 g (0.01a + ol) was added, the precipitated crystals were collected by filtration, and washed with methanol to obtain l-
3.5g of 13 was obtained.

λmax=600 nm, t=2.15 Methoxypropene 5.3g (0
, 04 mol) was added and heated under reflux for 1 hour (B).
CI! GOOR ■-22 (CgHs) 3.4g of compound (A) in 3N DMF50- (0°01m
ol) and acetic anhydride (0.015 mol) were added, and the mixture was heated and stirred for 10 minutes while keeping the reaction temperature at 1.00°C. 3.0 g (0.01m
ol) and triethylamine 4+d (0,03III
After the completion of the reaction, which was heated and stirred for 30 minutes while maintaining the reaction temperature at 100° C., the reaction solution was cooled to room temperature, and 200% of ethyl acetate was added to precipitate crude crystals.

This crude crystal was dissolved in methanol and NaPFh1.
7 g (0.01 mol) was added, the precipitated crystals were collected by filtration, and washed with methanol to give 1.7 g (0.01 mol) of ■-22.
I got g.

λvgax = 470 nm, t = 8.43X10' (methanol) The compound of general formula (1) is
~1000 ■ used, preferably 1~8 per rrr
00 ■ Used.

When using the compound of general formula (1) as a filter dye or antihalation dye, any effective amount can be used, but it should be used so that the optical density is in the range of 0.05 to 3.5. is preferable, and it may be added at any step before coating.

The compound of general formula (1) according to the present invention can be used in both emulsion layers and other hydrophilic colloid layers.

The fine particle dispersion of the compound of general formula (1) of the present invention can be prepared by a method of precipitating the compound of the present invention in the form of a dispersion, and/or by a known pulverization method in the presence of a dispersant, such as ball milling (ball milling). , vibratory ball mill, planetary ball mill, etc.), sand milling, colloid milling, jet milling, roller milling, etc. (in that case, a solvent (e.g., water, alcohol, etc.) may be present). I can do it.

Alternatively, after dissolving the compound of the present invention in a suitable solvent,
A microcrystalline powder may be precipitated by adding a poor solvent for the compound of the present invention, in which case a dispersing surfactant may be used, or the compound of the present invention may be first dissolved by controlling the pH. The microcrystalline particles of the compound of the present invention in the dispersion may have an average particle size of 10 μm or less, more preferably 2 μm or less, and particularly preferably 0.0 μm or less, and particularly preferably 2 μm or less. It is more preferable that the particle size is .5 μm or less, and in some cases, 0.1 μm or less.

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. In addition, particles (
For example, the emulsion may be a negative type emulsion), or it may be a grain mainly formed inside the grain (for example, an internal latent image type emulsion, a prefogged direct reversal type emulsion). Preferably,
These particles are such that the latent image is formed mainly six times.

The silver halide emulsion used in the present invention has a thickness of 0.05 mm.
A tabular grain emulsion in which grains having a diameter of 0.3 microns or less, preferably 0.3 microns or less, and an average ast coverage ratio of 3 or more occupy 60% or more of the total projected area; A monodisperse emulsion having a statistical coefficient of variation (value S/d obtained by dividing the standard deviation S by the diameter d in a distribution where the projected area is approximated by the diameter of a circle) is -0S or less is preferable. Further, two or more kinds of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsion used in the present invention is P. Grafkide, 2(
Chim+e erPh Photographic (Chim+e erPh)
ysique Photographique ) (
Published by Paul Montell, / 7 years], G, F, Ri.

Ia (G, F, Duffin), Photocratic Emulsion, Chemis)')-(Photo-
graphic emulsion chemist
y) (Published by 7 Orcal Press, /ri Otsunen), V, L Zelik-r:y (V, L, Zelikman) et al., Making and Coating Photographic jl-? Lujon (Making and Co.
atingPhotographic Emulsi
It can be prepared using the method described in ``On)'' (7 Orcal Press, / Hirotoshi Riotoshi).

In addition, during the formation of silver halide grains, in order to control grain growth, ammonia, rhodanpotash, rhodanammonium, thioether compounds (for example, U.S. Pat. No. 3, Core/17,
Same No. J, J74t, No. 421, Same No. 3, 70≠, 730
No., Hiroshi No. 2, 27゜≠37, Hiroshi No. 274, 274.37
), thione compounds (for example, JP-A No. 3-4217-0♂, JJ-777)
No. 37, etc.), amine compounds (e.g., JP-A No. 37), 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 cadmicum salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

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

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

Sac, Sci, Phot, Japan), AnoA,
Enzyme-treated gelatin as described on page 30 (L.66) may be used, or a hydrolyzate of gelatin 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 rogen compound (co,≠-dichloro-4-hydroxy-/,
3°! -triazine and its sodium salt, etc.) and active vinyl compounds (/, 3-bisvinylsulfonyl-coprobanol, /, Corbis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether or vinylsulfonyl groups in the side chain. hydrophilic colloids such as gelatin2)
It is preferred because it cures quickly and provides stable photographic properties. N
-Carbamoylpyridinium salts ((/-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.)
? Haloa, midinium salts (/-(/-chloro-/-pyridinomethylene)pyrrolidinium--s7talennulphonate, etc.) are also excellent in their fast curing speed.

The silver halide photographic emulsions used in the present invention may be spectrally sensitized with methi/dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, nutyryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pylori/nucleus, oxacili/nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nuclei, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, be/zoselenazole nucleus, K/zimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline as a core with a ketomethylene structure! -on nucleus, thiohydantoin nucleus, corchioxazolidine-1
μm dione nucleus, thiazolidine-λ, ≠-dione nucleus, rhodanine nucleus, thiobarbyl acid root, etc.! -Member heterosegmental rings can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbenzene compounds substituted with a nitrogen-containing heterocyclic ring group (e.g., U.S. Pat.
2/), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,7 Hiroshi J, 310), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3. T/! , No. 473, J, t/J, t'l/ No., J, A/7. -Ta! No. 3.63! , 727 are particularly useful.

The silver halide photographic emulsion used in this technology is used as an antifoggant during the manufacturing process of light-sensitive materials, during storage or photographic processing, or to stabilize photographic performance.
Various compounds can be included. That is, azoles such as benzthiazolicum salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino triazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially /-phenyl-j-mercaptotetrazole)
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxatri/thione; azaindenes, such as triazaindenes, tetraazaindenes (with % Hiro-hydroxy substitution (/).

3.3a, 7) tetraazaindenes), hantaazaindenes, 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 photographic material produced using the present invention may contain a water-soluble dye entirely in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation.

As such dyes, oxonol dyes, hemioxonol dyes, steryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethane dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. be. 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 one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as necessary. A preferred layer arrangement is, from the support side, in this order: red sensitivity, green +'X sensitivity and blue sensitivity, blue sensitivity layer, green sensitivity layer and red sensitivity 1 in this order, or blue sensitivity, red sensitivity and green sensitivity in this order. Furthermore, any emulsion layer having the same color sensitivity may be composed of one or more emulsion layers having different sensitivities to improve the attained sensitivity, or a three-layer structure may be used to further improve graininess.

A non-light-sensitive layer may be present between two or more emulsion layers having the same color sensitivity. A configuration may also be adopted in which emulsion layers of different color sensitivity are inserted between emulsion layers of the same color sensitivity. Sensitivity may be improved by providing a reflective layer such as fine-grain silver halide under the high-sensitivity layer, particularly under the high-sensitivity blue-sensitive layer.

Generally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. For example, infrared-sensitive layers may be combined to create a pseudocolor four-quality 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 as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin/ 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 made black for the purpose of blocking light. The thorny surface of these supports is generally coated with
Primed. The support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods can be used, such as dip coating, roller coating, curtain coating, and extrusion coating. As necessary, U.S. Patent Nos. Ko♂ issue and 3rd issue! Multiple layers may be applied simultaneously by the coating method described in Ori 4L No. 7 and the like.

The present invention can be applied to various color and black and white photosensitive materials. Color negative films for general use or motion pictures, color reversal films for slides or television, color positive films and color reversal films, color diffusion transfer type photosensitive materials and heat developable color photosensitive materials are examples. be able to. Research Disclosure, Boiled/7/23(/
by utilizing the three-color coupler mixture described in U.S. Pat. 6,≠Otsu/
No. and British Patent No. λ, 102. The present invention can also be applied to black-and-white photosensitive materials for X-rays and the like by using the black color-forming coupler described in No. /3 Otsu. Plate-making films such as lithography film or scanner film, X-ray film for direct/indirect medical use or industrial use, negative black and white film for photography, black and white photographic paper, 00M or regular microfilm, silver salt diffusion transfer type photosensitive materials, and The present invention can also be applied to pre-/door-type photosensitive materials.

When the photographic elements of the present invention are applied to color diffusion transfer photography, peel-apart (peel-a/e-1) type or
A-/63! No. Otsu, same≠r-33AP No. 7, Tokukai Shozo
-/J (integrated type as described in 7≠Q and British Patent/, 3!0.!-≠; It is possible to configure a film unit that does not require peeling.

The use of a polymeric acid layer protected by a neutralizing timing layer in either type of format described above is advantageous in increasing processing temperature latitude. 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 flashlight sources such as flashlights (or metal-burning flash bulbs) are common.

Gaseous, dye solution, or semiconductor lasers, light emitting diodes, and plasma light sources that emit light in the wavelength range from ultraviolet to infrared can also be used as the recording light source. Also, fluorescent surfaces (such as CRTs), liquid crystals (LCDs) emitted from fluorescent materials excited by electron beams, etc.? An exposure means that combines a linear or planar light source with a micro-shutter array using lanthanum-doped lead titanium zirconate (PLZT) can also be used. 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, amine phenol compounds are also useful, but p-phinidine diamine compounds are preferably used, and an example of a substitute thereof is 3-methyl-Hiro-amino-N,N-diethylaniline. , 3-methyl-Hiro-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-Hiro-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-g-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-toluenesulfo/acid. These diamines are generally more stable in their salt form than in their free form, and are therefore preferably used.

The color developer may contain pn buffers such as alkali metal carbonates, phocates 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,
Benzyl alcohol, polyethylene glycol, 4i7
development accelerators such as ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boro/hydride, auxiliary developers such as /-phenyl-3-pyrazolidone, tackifiers, aminopolymer Various chelating agents such as carboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and diphonocarboxylic acids, and antioxidants described in West German Patent Application (OLS) No. 1, No. 230 are used to develop color. It may be added to the developer.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybenzenes such as hydroquino, no-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known black and white developers such as amine phenols such as methyl-p-amine phenol can be used alone or in combination.

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

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (■), cobalt (lI), chromium (IV), and copper CI[), peracids, quinones, and nitrone compounds. Ferricyanide; dichromate; iron (If
f) or Kobal) (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Complexes of aminopolycarboxylic acids such as nitrilotriacetic acid, 3-diamino-pronognortetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; mar/gannates; nitronephenol etc. can be used. Of these, iron ethylenediaminetetraacetate (I
I[) salt, diethylenetriaminepentaacetic acid iron (I[I) salt and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediamide/iron tetraacetate CI) complexes are particularly useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. ♂23. ? ! ? No., West German Patent Tube 1
,2ri0. ? / Ko issue, same 2.0! the law of nature.

RT issue, JP-A-33-3273 issue, same! 3-! 7♂
37th issue, 37th Hiroshi/♂ issue, same! ! -6j731, same!
! -71 otsu No. 23, same J3-2!630, same j3-ta! Otsu 3/issue, same! 3-10g No. 232, same! ! -/ 2
'AlA2≠ issue, same! 3-/μ1623, same! 3-λ
♂4t2 Otsu No., Research Disclosure Boiled /7/
Compounds having a mercapto group or a disulfide group described in λ No. (July 7, 2007), etc.;
Thiazolidine derivatives as described in tO/No. 2; Tokuko Sho≠Yoichi! No. 306, Tokukai Sho! --λO♂No.32, same! No. 3-3273j, U.S. Pat. No. 3,701, i
Thiourea derivatives described in No. t1; West German Patent No. 1, /J
7,7/! No., Tokukai Akira! Iodide described in ♂-/Otsu-3J; West German Patent No. 24J, Hiro/θ No., Ko, 7 Hiro? , Hiro 3
Polyethylene oxides described in No. 0; Tokko Sho 4tt
- Polyamine compounds described in rtjJ issue; other JP-A Akihiro Terahiro Kohiro ≠ issues, intermediary ter! Ri6IA Hiro issue, same! 3
-2 Hiro Turf, Doyo Hiro-33727, Doyo 3-26
Compounds described in No. 304 and No. 304 and No. 304 and No. 304, as well as iodine and bromine ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are disclosed in I# Busy U.S. Patent No. 3. ♂rii
, RTR No., West German Patent No. J.

Kota O1! Noko-go, Tokukai Akira! Compounds described in No. 3-2jrtJO are preferred. Furthermore, U.S. Patent No. 4L! ! −♂３
Compounds described in ≠ are also preferred. These bleach accelerators may be added to the photosensitive material. Color photosensitive material ft for photography
These bleach accelerators are particularly effective when bleach-fixing.

Examples of the fixing agent include thiosulfates, thiocyanates, thioureas of thioether compounds, and large amounts of iodides, but thiosulfates are commonly used. Preservatives for bleach-fixing solutions and fixing solutions are preferably sulfites, bisulfite groups, or carbonyl bisulfite adducts.

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, and disinfectants and preventive agents that prevent the growth of various bacteria, algae, and molds. A pie agent, a metal salt such as a magnesium salt or an aluminum salt or a bismuth salt, a surfactant for preventing drying load or unevenness, and various hardening agents can be added as necessary. Or Photographic Science and Engineering by West (L, E, We
st, Phot, Sci.

Eng, ), Volume 3a4L~3ty-<-di(
/ At), etc., may be added. The addition of chelating agents and anti-piping agents is particularly effective.

In the washing process, two or more tanks of cypress are washed in countercurrent water to conserve water. Furthermore, instead of the water washing process,
-rma≠A multistage countercurrent stabilization treatment process as described in No. 3 may be performed. In the case of this step, a two-tank countercurrent column is required. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, the membrane p
Various buffering agents (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia) for adjusting H (e.g., H) , monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and aldehydes such as formalin can be cited as examples. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid,
acids, organic phosphoric acids, organic phosphonic acids, aminopolyphosphonic acids, phosphonocarzenic acids, etc.), bactericidal agents ((inzointhiazolinone, iriteazolone, Hirothiazoline benzimidazole, /・age/chemical phenol, null-7 anilamide, Various additives such as benzotriazole, surfactants, fluorescent whitening agents, hardeners, etc. may be used, and two or more compounds for the same or different purposes may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a membrane pH adjusting agent after treatment.

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

The washing and stabilization processing time of the present invention varies depending on the type of photosensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds or more! It's a minute.

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

For example, U.S. Pat. No. 3,3412. Indoaniline compound described in No. 7, No. 3,3≠2,322, Research Disclosure/≠? jO and J/3
Thick basic type compound described in No. 2, same/3ri! Aldol compounds described in ≠, metal salt complexes described in U.S. Pat.
! No., jJ-/l/, No. 33, j6-! No. 2234, No. j4-A7♂Hiro-, No. j4-1373, No. 3
Otsu-♂3733, same! t-r, issue 37.3, same! Bu-♂ri73! No., jj-4/137, j6-74
'Hiroshi 30, same! Bu-/Q Buko Hiro/No., same! A-107
23 Otsu issue, same! Examples include various salt-type precursors described in No. 7-27!37 and No. 77-43-43.

The silver halide color light-sensitive material of the present invention may contain various /-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are %Kaishojj-4ko 33rd No. J'7-/41413
Hiro 7, same! 7-. 2///Hiroshi 7, 11-30!3
No. 2, same rr-, ros36, same j♂-30!33, same j,! '-70j3≠ issue, same! ♂－! Issue 033j and the same! ? -//j≠It is described in No. 31, etc.

Various treatment liquids in the present invention are used at 100 cmro0c. The standard temperature is 33°C or 3♂"C, but it is possible to accelerate the processing by increasing the temperature to a higher temperature and shorten the processing time, or conversely by setting the temperature to a lower temperature to improve image quality and improve the stability of the processing solution. Furthermore, cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 1, ujj, 770 or U.S. Pat. You may also perform other processing.

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

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

When the light-sensitive material of the present invention is a color paper, it can be bleach-fixed as required, very generally, and even when it is a color photographic material for projection.

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

Example 1 (Preparation of silver halide emulsion) 32 g of lime-treated gelatin was added to 1000 g of distilled water,
After dissolution at 40°C, 3.3g of sodium chloride was added and the temperature was raised to 52°C. Add N, N' to this liquid.
-Dimethylimidasolysine-2-thione (1% aqueous solution) was added for 3.2 d. Next is nitric acid! ! A solution prepared by dissolving 32.0 g in distilled water 200 g and sodium chloride I1. Og
A solution prepared by dissolving 100 ml of 200 mL of distilled water was added to and mixed with the above solution over 14 minutes while maintaining the temperature at 52°C. Furthermore, a solution of 128.0 g of silver nitrate dissolved in 560 g of distilled water, 44.0 g of sodium chloride, and hexachloroiridium (TV
) A solution prepared by dissolving 0.1 μm of potassium acid in 560 μm of distilled water was added and mixed over 20 minutes while maintaining the temperature at 52°C. After being kept at 52°C for 15 minutes, the temperature was lowered to 40°C, and desalination and water washing were performed. Further, lime-treated gelatin was added to obtain emulsion (A). The resulting emulsion had an average grain size of 0.
It contained cubic silver chloride grains of 45μ and a coefficient of variation of grain size distribution of 0.08.

In emulsion (A), the sodium chloride aqueous solution added together with the silver nitrate aqueous solution was replaced with a mixed solution of sodium chloride and potassium bromide (the total number of moles was the same, the molar ratio was 98:2).
A silver chlorobromide emulsion (B) containing 2 mol % of silver bromide was obtained by changing the emulsion to 2 mol % of silver bromide. The addition time of the reaction solution was adjusted so that the average grain size of the silver halide grains contained in the emulsion was equal to that of emulsion (A). The obtained particles were cubic, and the coefficient of variation in particle size was 0.08.

In emulsion (A), by changing the sodium chloride aqueous solution added together with the silver nitrate aqueous solution to a mixed solution of sodium chloride and potassium bromide (the total number of moles was the same and the molar ratio was 9:1), 10 A silver chlorobromide emulsion (C) containing mol % of silver bromide was obtained. The addition time of the reaction solution was adjusted to UFJ so that the average grain size of the silver halide grains contained in the emulsion was equal to that of emulsion (A). The obtained particles were cubic, and the coefficient of variation in particle size was 0.09.

After adjusting the pH and PAg of the three emulsions thus obtained, triethylthiourea was added to optimally chemically sensitize each emulsion, (A-1), (B-1) and (C-1).
) was obtained.

Apart from this, a fine-grain silver bromide emulsion with an average grain size of 0.05μ (a-1: 2.5X10-
'mol of potassium hexachloroiridate (rV)) was prepared.

After adding emulsion (a-1) in an amount equivalent to 2 mol % of silver halide to emulsion (A), triethylthiourea was added to prepare an optimally chemically sensitized emulsion.
-2).

These four types of silver halide emulsions each contained the following compounds as stabilizers at 5.0XI per mole of silver halide.
O-' moles were added.

Stabilizer (it) The halogen composition and distribution of the four types of silver halide emulsions obtained were investigated by X-ray diffraction.

As a result, emulsion (A-1) was a 100% silver chloride emulsion (
B-1) exhibited a single diffraction peak of 98% silver chloride (2% silver bromide), and emulsion (C-1) exhibited a single diffraction peak of 90% silver chloride (lO% silver bromide). On the other hand, for emulsion (A-2), in addition to the main peak of 100% silver chloride, 70% silver chloride (
30% silver bromide), 60% silver chloride (11 bromide)
A broad sub-peak with a tail around 40%) could be observed.

(Dispersion of Solid Fine Particles of Compound of the Present Invention) Crystals of the compound of the present invention having the following composition were kneaded and ground into fine particles (having an average diameter of 0.15 μm or less) using a sand mill. Further, 0.1 g of citric acid was dispersed in a 10% lime-treated aqueous solution of gelatin, and the sand used was removed using a glass filter. The compound of the present invention adsorbed on the sand on the glass filter was also washed off using hot water to obtain a 7% aqueous gelatin solution. This is used as a solid fine particle dispersion of the compound of the present invention.

Dispersion A Compound of the present invention (1-2) 0.8 g (15) 1.5 g Surfactant (Cpd-10) 5% aqueous solution 5-Dispersion B Compound of the present invention (1-13) 0.8 g ( 1-1
4) 1. 5g Surfactant (Cpd-10) 5% aqueous solution 5-Dispersion C Compound of the present invention N-2) 0.8g Surfactant (Cpd-11) 5% aqueous solution 5ml (Preparation of color photosensitive material) Next An emulsified dispersion of a coupler and the like was prepared, combined with each A silver halide emulsion, and coated on a paper support laminated on both sides with polyethylene to produce a multilayer color light-sensitive material having the layer structure shown below.

(Layer structure) The composition of each layer is shown below. The numbers represent coating 1 (g/bo; -/e for solvents), and the silver halide emulsions represent coating amounts in terms of silver.

Polyethylene laminated paper [contains a white pigment (Tie) and a blue dye (ulmarine) in the polyethylene of the emulsion layer] Halesine gelatin dye (solid fine particles h) Yellow silver halide emulsion (Table 1) Spectral sensitization Dye (Table 1) Yellow coupler (Y-1) Color image stabilizer (Cpd-7) Solvent (Solv-6) Gelatin: 0 Gelatin filter dye (Dye-4) Color mixing inhibitor (Cpd-4) Solvent (Solv) -2) (Solv-5) Mazene silver halide emulsion (Table 1) 0, 80 (Table 1) 0, 30 0, 12 Spectral sensitizing dye (Table 1) Supersensitizer (Table 1) ) Magenta coupler (M-1) Magenta coupler (M-2) Color image stabilizer (Cpd-1) (Cpd-8) (Cpd-9) Solvent (Solv-1) Solvent (Solv-2) Gelatin No. 11 】Five Plate Bean Double ■Y Gelatin filter dye (Dye Ultraviolet absorber (UV-1) Color mixture prevention agent (CPd-4) 8 medium (Solv-3) Silver halide emulsion (Table 1) Spectral sensitization Dye (Table 1) Supersensitizer (Table 1) 5) Cyan coupler (C-1) 0.32 color image stabilizer (Cp d-5) O,'l 7 (Cpd
-6) 0.04 (Cpd-7) 0.40 Solvent (Solv-4) 0.15 Gelatin 1.34 Gelatin
0.53 Ultraviolet absorber (UV-1)
0116 Color mixing inhibitor (Cpd-4) 0.
02) 8 medium (Solv-3)
0. 09'l1lJL Kobo 1'' D- Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%) 0.17 Liquid paraffin 0.03 As a gelatin hardening agent for each layer, ■-oxy-3.5- 14.0 g of dichloro-5-) riazine sodium salt was used per 1 g of gelatin.

yellow coupler (Y-1) Cyan coupler (C-1) E R=CiHs, CaHqO and H i 2:4:4 mixture (weight ratio) of Magenta coupler (M-1) magenta coupler (M-2) Color image stabilizer (Cpd-1) Color image stabilizer (Cpd-5) H CaH cry 01( CaF2(t) CaHq<t) 2: =4 mixture (weight ratio) Color image stabilizer (Cpd-6) H Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) H H Color mixing inhibitor (Cpd-4) B Color image stabilizer (Cpd-7) Thousand CH, -CH,.

C0NHC*Hv(t) Color image stabilizer (Cpd-8) CsH++(t) Color image stabilizer (Cpd-9) Surfactant (Cpd-10) Surfactant (Cpd-11) Supersensitizer (Cpd-12) (Cpd-13) CHz-CI-CHz Solvent (S.

IV 1) 0 = P+OCHzCHCaHq)sCaH9(t) 0)1 CaHq(t) Yell t per mole of silver halide 3゜ 2×10 'mo1 2゜ 7 X 1 0-’mol Solvent (S.

IV-2) Solvent (Solv-3) COOC5HI? (CHHz) * C00C,H,.

Solvent (Solv-4) Solvent (Solv-5) Solvent (Solv 6) 0=P-(-0 C*H+w(iso))i Ultraviolet absorber (UV the law of nature H CsHIICt) ye2 3° per mole of silver halide 5×10 mol Added.

and Cpd-12 at 2° 6X10-”Mo Lu/Ag was used in combination.

ye3 1° per mole of halogenated i 7×10-’mol and Cpd-12 at 2° 6X10-3 mol/Ag Cpd-13 was used in combination with 1X10-' mol/Ag.

(Dye-4) 10cm per coating film (for filter and irradiation prevention) (Dye-4)
-5) (CHz)a (CHz)n 0s- SO, 5■ per coating film (for filters and irradiation prevention) Table 1 (
Continued) The number in parentheses after the dye number represents the coating amount (■/A).

The above samples were exposed to laser light. For samples using Dye-1, Dye-2, and Dye-3 as sensitizing dyes, a laser exposure device designated as exposure device-1 was used.

The exposure apparatus used in the examples is shown below.

(Exposure apparatus-1) As lasers, semiconductor laser ^lGa1nP (oscillation wavelength, approximately 670 nm), semiconductor laser GaAlAs (
(oscillation wavelength, approximately 750 nm) and GaAlAs (oscillation wavelength, approximately 830 nm). An apparatus was constructed in which the laser beams were sequentially scanned and exposed onto color photographic paper, which was moved in a direction perpendicular to the scanning direction using a rotating polyhedron. The exposure amount was electrically controlled by the exposure time of the semiconductor laser. (The exposure apparatus used in the present invention is detailed in the specification of Japanese Patent Application No. 63-226552 filed by the present applicant.) Using the above-mentioned exposure apparatus-1, semiconductor laser beams with luminous flux wavelengths of about 670 nm, about 750 nm, and about 830 nm are used. The output was adjusted and exposure was carried out so that the width of each line was about 50 μm. It was developed through the processing steps shown below.

On the other hand, each sample was closely attached to a CTF measurement chart and exposed to light for resolution measurement. The illumination used was a xenon light source with maximum transmission wavelengths of 670 nm, 750 nm, and 830 nm of a bandpass filter IF-3 type manufactured by Nippon Vacuum Optics.
The light was passed through each nm filter, and the amount of light was adjusted using an ND filter. The exposure time was approximately 10-4 seconds. It was developed through the processing steps shown below. The density of the obtained yellow magenta and cyan colored images was measured using a micro reflection densitometer with an aperture of 5 μm x 400 μm to obtain a CTF curve.

The sharpness of the edge of the line drawing obtained by exposure with semiconductor laser light and the number of lines of 7 m at a CTF value of 0.5
The values are shown in Table 2.

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

Processing process 1-Technical Poetry-Dish color development 35℃ 45 seconds bleach fixing
Rinse at 30-35°C for 45 seconds■ Rinse at 30-35'C for 20 seconds■ Rinse at 30-35°C for 20 seconds■
Rinse for 20 seconds at 30-35°C■ 30-35°C
Dry for 20 seconds, 60 seconds at 70-80'C (rinse)
→■ The 3-tank countercurrent direction was set to 2. ) The composition of each treatment liquid is as follows.

Sadate Niri l Okasui 800d
Ethylenediamine-N,N.

N',N'-tetramethylphosphonic acid 1.5g triethylenediamine (1゜4diazabicyclo(2,2゜2)octane) 5.0g sodium chloride 1.4g potassium carbonate
25g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate N,N-diethylhydroxylamine fluorescent brightener (UVITEX CK, manufactured by Ciba-Geigi) Add water and adjust the pH ( 25°C) 1 foot 1 water Ammonium thiosulfate (70%) Sodium sulfite Iron(III) ethylenediaminetetraacetate Ammonium ethylenediaminetetraacetate disodium Ammonium bromide Add water and PHC 25°C) 5°g 4° g 2゜g 000d 10.10 00m 00m 8g 5g g 0g 000m 5.5 Ion exchange water (calcium, magnesium 3pp each
m or less) According to the present invention, resolution and edge sharpness can be significantly improved. In particular, samples 4 and 6 are yellow,
Sample 6, which shows excellent edge sharpness across magenta and cyan color images, has a slightly low sensitivity in the second layer (cyan color development), but also has high chroma especially in yellow, magenta, and cyan color images (color An excellent image was obtained (with good separation).

In addition, none of the samples of the present invention had any color staining due to residual color caused by the compound of the present invention, and the same degree of color development as Sample 1 of the comparative example was obtained.

Example 2 50 g of gelatin was dissolved in water, and 30 d of a 4% by weight aqueous solution of sodium dodecylbenzenesulfonate was added as a surfactant, and 1% by weight of 1-hydroxy-3,5-dichlorotriazine sodium salt was added as a hardening agent. 45 minutes of an aqueous solution was added, and then the following solid fine particle dispersion of the compound of the present invention was added. That is, the crystals of the compound of the present invention are kneaded and made into fine particles (the average diameter of which is 0.15 μm or less) using a sand mill.
It was crushed. Furthermore, 10% by dissolving 0.1g of citric acid.
The sand used was removed using a glass filter by dispersing it in a 25-mL aqueous solution of lime-treated gelatin. Compounds adsorbed on the sand on the glass filter were also washed away using hot water to obtain a 7% aqueous gelatin solution.

Dispersion A Compound (1-9) of the present invention1. og Surfactant (Cpd-10 of Example 1) 5% aqueous solution 5g Dispersion B Compound of the present invention (1-14) 1. 0g surfactant (Cpd-10 of Example 1) 5% aqueous solution 5-Meanwhile, for comparison, a solution of dye a below was added to I-8 above! -27 was added in the same amount to make a total amount of 1i. This gelatin-containing aqueous solution was applied onto a paper support coated with polyethylene so that the dry film thickness was 4 μm. On the other hand, the following D
Add 50d of 0.05% by weight methanol solution of ye-7, and add 50d of 0.05% by weight methanol solution of Cpd-12 of Example 1 30-1 0.5% by weight solution of Cpd-13 of Example 1 20- and 0.6% by weight solution of Cpd-14 below 40
d and further added 4.0% by weight aqueous solution 30- of sodium dodecylbenzenesulfonate, and
35N1 of a 1.0% by weight aqueous solution of 5-dichlorotriazine sodium salt was added, stirred, and coated on the gelatin-coated surface of the support. Furthermore, an aqueous solution containing gelatin and sodium dodecylbenzenesulfonate was applied as a protective layer thereon.

The film thus produced was exposed to light using (A) a 760 nm light emitting diode (B) and a 783 nm semiconductor laser, using an automatic processor FG-80ORAC (manufactured by Fuji Photo Film Co., Ltd.) using a developing solution LD-835 (manufactured by Fuji Photo Film Co., Ltd.). Treatment was performed at °C for 20 seconds.

Image quality rating: 1 (Very poor image quality with many fringes)
Evaluation was made on a 5-point scale from 1 (very much residual color) to 5 (no residual color) to 5 (sharp image). In the case of evaluating fringe and residual color, visual observation can be more sensitive than measurement using an instrument, and visual evaluation is also performed in actual use of photosensitive materials.

The results are shown in Table 3.

pd-14 CHz CH=CIIz Comparative dye a is the following dye described in British Patent No. 434,875.

C113CH31' As is clear from Table 3, when the dispersion of the present invention is used, images with good image quality and less residual color can be obtained.

Example 3 [11 Preparation of tabular silver iodobromide grain emulsion 5 g of potassium bromide and 0.05 g of potassium iodide in 1N water
, 30 g of gelatin, thioether HO of the following structural formula (
CHri2S(CH2)2S(CH2)20HO,125
An aqueous solution of 8.33 g of silver sulfate, 5.94 g of potassium bromide,
An aqueous solution containing 0.726 g of potassium iodide was added in 45 seconds using a double jet method. Next, potassium bromide 2.
After adding 5 g of nitric acid, an aqueous solution containing 8.33 g of nitric acid was added for 7 minutes and 30 seconds until the flow rate at the end of the addition was 2
It was added to double the amount. followed by silver nitrate 153.3
4g of an aqueous solution and an aqueous solution of potassium bromide at a potential of pAg.
2 using the controlled double gent method while keeping s at 1.
It was added for 5 minutes to allow the particles to grow. 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% potassium iodide aqueous solution was added.
cc was added over 30 seconds. After this, increase the temperature to 35°C
After removing soluble salts by sedimentation method,
The temperature was raised to °C, 68 g of gelatin, 2 g of phenol, and 7.5 g of trimethylolpropane were added, and the pH was adjusted to 6.40 and pAg to 8.45 with sodium hydroxide and potassium bromide.

After raising the temperature to 56°C, sensitizing dye 6 with the following structure was added.
20■ and 4-hydroxy-6-methyl-13,3a,?
- 160 μm of tetrazaindene were added. After 10 minutes, 8.2 inches of sodium periosulfate 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 consisted of grains with an aspect ratio of 3 or more, and the average projected area diameter of all the grains with an aspect ratio of 2 or more was 0.83 μm, with a standard deviation of 18.5. %, the average thickness is 0.161 μm, 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 per mole of silver halide to the emulsion described in [1] to prepare a coating solution.

2.6-bis(hydroxyamino)-4-diethylamino-1,3,5-) riazine 80■ 1.4-dihydroxy-3-botacium sulfate 9.3g Sodium polyacrylate (average molecular weight 14° 10,000):
4. Preparation of Og[31 Surface Protective Layer Coating Solution As the surface protective 8i layer coating solution, an aqueous solution having the following composition per side upon drying was used.

Gelatin 1.2g/rrf dextran 0.4g/polyacrylamide 0.4g/sodium ivoryacrylate
0.02g/Povolystyrenesulfonic acid potassium 0.02g/Popoly (methyl methacrylate/methacrylic acid; molar ratio 9:1) C particle size 4.3μ) 0.05g/podimethylsiloxane (dispersed with dodecylbenzenesulfonic acid) ) (particle size 0.11 μ) 0.03 g/nr Cetyl palmitate (dispersed with dioctyl sodium α-sulfosuccinate) Particle size 0.10 μ 0.03 g/n? Colloidal silica 0.15g/potassium dinitrate 0.06g/bo α-sulfosulfosulfonic acid dioctyl sodium salt 0.005g/pododecylbenzenesulfonic acid 0.005g/bo p-octylphenoxyethoxyethoxyethoxyethoxyethanesulfonic acid sodium 0.005g/po Sodium p-octylphenoxytriglycidylbutanesulfonate 0.005g/m Poly(degree of polymerization 10) Oxyethylene cetyl ether 0.02g/Bopoly(degree of polymerization 10) Oxyethylene poly(degree of polymerization 3) Oxydiglyceryl octyl ph22 Polyether 0.005g/Bovoli (degree of polymerization 10) Oxyethylene poly(degree of polymerization) Glyceryl cetyl ether 0.005g/Bovoli (degree of polymerization 10) Glyceryl dodecyl ether 0.005g/rd Poly(degree of polymerization 10) Glyceryl p-nonylphenyl Ethyl 0.005g/BoCI 11
? CeH+? SOJ +CLCIIzO)-(CIlz)
4sOJa (n″, 4) 0.002g/rrI Jt Ca11+tSOz-N+C11zCIIzO+ 1l
) I (n # 16) 0.005 g/bo 4-hydroxy-6-methyl-13,3a,7-chitrazaindene 0.03 g/bo [41 Application of undercoat layer to support Biaxially stretched 175 μm thick A corona discharge treatment was performed on the polyethylene terephthalate film, and a coating amount of 5.5% of the first undercoating liquid having the composition shown below was applied. The first undercoat layer was applied in the same manner on the opposite side of the zero layer, which was coated using a wire bar coater to give Ice/rrf and dried at 175° C. for 1 minute.

[5] Method for producing solid fine particle dispersion of dye The compound (1-21) of the present invention was subjected to ball mill treatment by the following method.

Zirconium oxide beads were added to the mixture of water, surfactant TriLon-X-2000, and dye, the container was tightly capped, and the contents were ground in a mill for 4 days. Thereafter, the contents were dispersed in an aqueous gelatin solution, 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 is 1/
1, the amount of dye in 100g of gelatin dispersion is 1.4g
It was hot.

[Coating a subbing layer of a solid fine particle dispersion of dye 61 on a support”
On the first undercoat layer on both sides of the cloth [4], a second undercoat liquid having the following composition was applied in an amount of 8.5cc/
The undercoated film was completed by coating one side at a time and drying on both sides so as to obtain the rd.

Second base coating liquid-4 Gelatin 10g matting agent (
Polymethyl methacrylate with an average particle size of 2.5 μm) 0.3 g Ca Hq (C! Hs + CHCHt OCOC
HtC4H9(CzHs+CHCHzOCOCHS 0
3N ao, 2g Solid fine particle dispersion of [51 above] 12.0g (as the dye itself) Dye with the following structural formula (emulsion form) (4%) 27.45gHsl;z
Add water to Ltlls and above to obtain Il.

[71 Preparation of photographic material] The emulsion coating solution of [2] and the surface protective layer coating solution of [3] were co-extruded to form a polyethylene terephthalate support coated with an undercoat layer of [61] as shown in Table 1. Apply to both sides in the same way, dry, and apply photographic material 3-
It was set to 1.

In addition, photographic materials 3-2 to 3-8 were prepared by changing the solid fine particle dispersion in the second undercoating liquid to each compound listed in Table 1 in photographic material 1-1. In this case, for each material, the amount of silver coated per both sides was 4.0 g/rrr (2.0 g/rrr per one side), and the amount of gelatin coated in the surface protective layer per one side was 1.0 g/rrr as shown in [3]. It was 2g/rrf. In the photographic material manufactured by Matasupe, 1°2-bis(sulfonylacetamido)ethane was added as a hardening agent to the emulsion layer at a ratio of 6 m+*ol/l OOg gel immediately before coating.

(Photographic performance evaluation) For exposure of photographic materials 3-1 to 3-8, G-
Four screens were used. Photographic materials 3-1 to 3-8 were tightly sandwiched between two sheets of G-4 screen according to a conventional method, and exposed to X-rays through a 10 cm water fan dome.

For processing after exposure, use Fuji Photo Film's RD-
Automatic processing was carried out using 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 material 3-8 set as 100.

(Measurement of Sharpness (MTF)) The MTF was measured using the combination of the above-mentioned 64 screen and automatic processor processing. MT measured with a 30 μm x 500 μm aperture with a spatial frequency of 1.0 cycles/-
Evaluation was made using the F value at a portion where the optical density was 1.0.

(Evaluation of residual color) The residual color of the film after treatment was evaluated as follows.

The above materials were first processed in an FPM-4000 automatic processor without exposure to light. However, in order to deteriorate the conditions, a used developer having a paper pH was used, and the development temperature was set at 31°C and the washing water temperature was set at 10°C. Subsequently, the unexposed sample was processed in the same manner for 90 seconds at FPM ~ 4000 using a developing solution in a normal state at a developing temperature of 35 DEG C. and a washing water temperature of 25 DEG 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 property was visually evaluated. As a result, there is virtually no difference in residual color (A), the former is slightly inferior (B), and the former is slightly inferior, but considering the mandatory conditions, it is within the acceptable range (C
), the former is inferior and unacceptable (D), the former is very inferior (E
) and ranked them.

The results are shown in Table 4.

The present invention utilizes conventional solid state dispersion methods (3-4 to 3).
-6), it is particularly superior in terms of residual color, and although the force uniform dispersion type (3-7) has excellent residual color,
TF was inferior.

Table 4 Comparative Compound 1 Compound described in JP-A-63-197943 OOH Comparative Compound 2 Compound described in JP-A-64-40827 * Comparative Compound 4 was dissolved during dispersion and became uniform.

C00I+ OOH Comparative compound 3 Compound described in JP-A-52-92716 Comparative compound 4 Compound described in JP-A-63 No. 244034 Example 4 After corona discharge treatment on a paper support laminated on both sides with polyethylene, Paper support samples A, B and C were prepared using a gelatin subbing layer or a dispersion of the compounds of the invention described below.

(Dispersion method of the compound of the present invention) The following crystals of the compound of the present invention were kneaded and made into fine particles using a sand mill. Further, 0.5 g of citric acid was dispersed in a 10% lime-treated gelatin aqueous solution 251R1, the used sand was removed using a glass filter, and the compound of the present invention was added to the sand on the glass filter! -41.6g Compound of the present invention 1-19 1. 0g (surfactant) 5rn1 The attached compound was removed and 100d 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/M Paper support B
Antihalation layer gelatin 0.6 g/M Compound of the present invention 1-4 40 mg/B Compound of the present invention 1
-19 25+ng/rd Paper support C, antihalation layer gelatin 0.6 g/a Compound of the present invention 1-4 65 ng/A Compound of the present invention 1-
19 40 mg/rrr Multilayer color photographic paper sample 4- with the layer configuration shown below on paper support samples A, B and C.
I got 1 to 44.

The coating solution was prepared as follows.

7-- Amount of ゞ, -1' Yellow coupler (ExY) 19. Ig and color image stabilizer (Cpd-1) 4.4g and (Cpd-7) 1.8
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 (88 g).
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing cc. On the other hand, silver chlorobromide emulsion (80.0 mol%, cubic,
Average particle size 0685μ, coefficient of variation 0.08 and bromide 1!80.0 mol%, cubic, average particle size 0
．． 62μ with a coefficient of variation of 0.07 at a ratio of 1:3 (
A sulfur-sensitized product was prepared by adding the following blue-sensitive sensitizing dye in an amount of 5.0 x 10-' mol per mol of silver. 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 the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. l-oxy-3,5-dichloro-5-) riazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral enhancing dyes were used in each layer.

03-3Odl・N(CJs)s (per mole of halogenated tli?, 0X10-' mole) (Silver halide) 4° and oxt per mole.

4 mol) (0.9XlO-'' mol per mol of silver halide) For the red-sensitive emulsion layer, add the following compound to 1 mol of silver halide.
2.6 x 10-'' moles were added per mole.

of comparative dyes were added.

In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, ■-(5-methylureidophenyl)5-mercaptotetrazole was added at 4% per 1 mole of halogen.
．． 0x10-6 mole, 3.0x10-S mole, 1.0X
IO-'mo/L/, and 2-/thi-5-tert-octylhydroquinone were added at 8X10-' mole, 2XIO-'', and 2X10-'' per mole of halogenated i, respectively.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, and 7-titrazaindene were added at 1.2×10
-'' mol, 1.1X10-' mol was added.

One of the paper support samples contained the following 8 mg/ml in its emulsion layer:
r+ (and (N configuration) The composition of each layer is shown below. The numbers are coating 1 (g/n()
The silver halide emulsion that represents! Represents I-converted coating amount.

Four types of samples A, B, and C were prepared by providing an undercoat layer and an antihalation layer on 111 pieces of polyethylene laminated paper [the first layer of polyethylene contains a white pigment (TiO□) and a bluish dye (ulmarine)].

Ni1 Yu Huang IL The above-mentioned silver chlorobromide emulsion (AgBr: 80 mol%) 0.26 1.83 0.83 0.19 0.08 0.18 18 Gelatin yellow coupler (ExY) Color image stability 11 ( Cpd-1) 〃' (Cpd-7) Solvent (Solv-3) (Solv-6) Gelatin color mixing inhibitor (Cpd-6) Solvent (Solv-1) (Solv-4) No. 1, JL Kogyo 31D - 0,99 0,08 0,16 0,08 Silver chlorobromide emulsion (AgBr 90 mol%, cubic, average grain size 0.47 μ, coefficient of variation o, 12 and AgB
r90 mol%, cubic, average particle size 0.36μ, coefficient of variation o,.

9 in a ratio of 1:1 (Ag molar ratio))
0.16 gelatin
1.79 magenta coupler (ExM)
0.32 Color image stabilizer (Cpd-3) 0.
20 (Cpd-8) 0103 〃 (Cpd-4) 0.01 (Cpd-9
) o, 04 Solvent (Solv-2) 0.65 Gelatin 1.58 Ultraviolet absorber (UV
-1) 0.47 color mixing inhibitor (Cpd-5)
0.05 solvent (Solv-5)
0.24 Male U Engineering Red 311- Chlorobromide 11 (AgBr70 mol%, cubic, average particle size 0.49μ, coefficient of variation 0.08 and AgBr7
Gelatin 1.34 Cyan coupler (ExC) 0.30 Color image stabilizer (Cp
d-6) 0.17" (Cpd-7)
0.40 solvent (Solv-6)
0.207'J-ν Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing prevention agent (Cp
d-5) 0. Solv-5
) 0. 081 Upper 1 unit gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0,03 (Cpd-1) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer H (Cpd 5) Color mixture prevention agent H (UV-1) Ultraviolet absorber H CsH++ (t) H c, uq (t) H CJ* (t) of 4: 2 = 4 Mixture (N amount ratio) (Solv-1) Solvent 2:4:4:Mixture (weight ratio) (Cpd-7) Color image stabilizer 1,000 CHI-CH2 CON HCaH*(t) Average molecular weight 80゜00 (Cpd-8) Color image stabilizer (Cpd-9) Color image stabilizer (Solv 2) 2:1 mixture of solvent (volume ratio) (Solv 3) Solvent 0 = Pro C9H + q(iso)) s(Sol
v 4) Solvent (Solv 5) Solvent COOCaH, q (CHi) a COOCaH+q (Solv 6) Solvent (ExC) Cyan coupler (Ex Y) Yellow coupler (ExM) Magenta coupler obtained samples 4-1 to 4-4 Regarding the photosensitometer (manufactured by Fuji Photo Film ■, FWH type, color temperature of light source 3.20
Stepwise exposure for sensitometry was provided through blue, green, and red filters using 0' K). On the other hand, exposure was performed to measure resolution (CTF), and then the following development treatment was performed. The concentration of the obtained sample was measured and the results shown in Table 5 were obtained.

(Processing process) Processing process Color development, bleaching, fixing water, washing, drying, drying (processing solution) Main Buddhist indigo water, diethylenetriamine, pentaacetic acid, nitrilotriacetic acid, l-hydroxyethylidene-1,1-diphosphonic acid (60% solution), benzyl alcohol, diethylene glycol Sodium sulfite Potassium bromide Potassium carbonate N-Ethyl-N= (β-Meta, daytime - degree 37°C 33°C 24-34°C 70-80°C Kaji" ■ 3 minutes 30 seconds 1 minute 30 seconds 3 min 1 min 00d 1, 0g 2, 0g 1, 〇- 5d 1 〇- 2, Og 1.0g 0g sulfonamidoethyl) -3-methyl-4-amine aniline sulfate 4.5g hydroxylamine sulfate 3. 0g optical brightener (WHITE
X4゜Sumitomo Chemical) Add 1.0g water 1000100O (25℃)
IQ, 251 feet, 400M
1 Ammonium thiosulfate (70%) 150ml Sodium sulfite 18g Iron (1) ethylenediaminetetraacetate Ammonium 55g Disodium ethylenediaminetetraacetate 5g Add water 1000mfp100O°C)
6.70 Washing Water Ion-exchanged water tap water was deionized using an ion-exchange resin to reduce the calcium and magnesium content to 3 ppm or less, and 20 PPm of sodium isocyanurate dichloride was added before use. .

The pH of this water was 6.6.

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

Rapidly developable color photographic paper (EP No. 2734) obtained by using support samples B and C and providing a high silver chloride emulsion layer thereon.
29, 273430 and Japanese Patent Application No. 63-7861), similar results can be obtained.

Example-5 The blue-sensitive emulsion used in Example-4 had a silver bromide content of 0 and 6.
Mol% silver chlorobromide emulsion (cubic, average grain size 0.8
μ, coefficient of variation 0.08), a green-sensitive emulsion with a silver bromide content of 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 with a silver bromide content of 1°5 mol% (cubic, average grain size 0.45μ coefficient of variation 0.07). Samples 5-1 to 5-4 corresponding to samples 4-1 to 4-4 were prepared in the same manner as in Example-4.

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

(CHHz) * (C1h)4SO3H-N(CZIIS)3SO,.

(2゜5x10'' mole per mole of halogenated S!) and (2゜5x10'' mole per mole of halogenated S!) Cpd-10 50ff-5OJ-N (CxHs) s (4.0 x 10-' moles per mole of silver halide) and (7°0 x 10-' moles per mole of silver halide) (5 x 10-' moles per mole of silver halide in each emulsion).
4 mol was added. ) Using the obtained sensitive material, the same test as in Example 4 was conducted using the following processing solution and processing steps, and Sample 5-3.5-4 was the same as Sample 5.
The red sensitivity layer, the green sensitivity layer, and the sensitivity were higher than that of -2. In addition, Da+in of Samples 5-3 and 5-4 was as low as that of Samples 5-2, and the resolution was higher than the other samples as shown below.

Table 6 (O8 9X 10-' mol per 1 mol of halogenated S) Wing JLII, Monthly 1-degree Elbow-Mochi color development 35"C 45 seconds Bleach fixing 30-36°C 45 seconds stable ■ 30-37°C 20 seconds Stable ■ Stable at 30-37°C for 20 seconds ■ Stable at 30-37°C for 20 seconds ■ Drying at 30-37'C for 60 seconds (Stable) ■ →
■ A four-tank countercurrent system was adopted.

The composition of each treatment liquid is as follows.

Keisaku left standing position water Ethylenediaminetetraacetic acid triethanolamine sodium chloride potassium carbonate N-ethyl-N-(β-meta (sulfonamide ethyl) -3-methyl-4-amino Aniline sulfate 5.0g 800- 2.Og 8゜Og 1.4g 25.0g ) N,N-diethylhydroxy Ruamino 5.6-cyhydroxybenze N-1.2. 4-1-Lisle fonic acid Fluorescent brightener (4,4'-dia minostilbene series) add water H 2) Watada 1 hill water Ammonium thiosulfate (70%) sodium sulfite Iron ethylenediaminetetraacetate mouth 1 ammonium Ethylenediaminetetraacetic acid dibasic acid thorium add water H 4.2g 0.3g 2.0g 000m 10.10 400- 100- 8g 5g g 000d 5.5 An accident.

Formalin (37%) 0.1 g Formalin-sulfite adduct 0.7 g 5-chloro-2-methyl-4-isothiazolin-3-one 0
．． 02g 2-methyl-4-isothiazolin-3-one 0.018 Add water
1o00dPH4,0 Example-6 On a subbed cellulose triacetate film support,
Sample 601, which is a multilayer color fluorescent material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in g/rd unit of silver for silver halide and colloidal silver, and the amount expressed in g/rd unit for coupler additive and gelatin. Regarding the dye, the number of moles is expressed per mole of halogenated 8ml 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 (Haley silane prevention layer) Black colloid g O, 15 gelatin 1.9UV-1 (ultraviolet absorber) 0.03UV-2 (ultraviolet absorption M)
0.06UV-3 (ultraviolet absorber)
0.07Solv-2 (solvent) O,
0SExF-1 (cyan dye) 0.01E
xF-2 (cyan dye) 0.01 second layer (
#, sensitivity red circle emulsion layer A 14 mol%, uniform equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, diameter/thickness ratio 3.0 Coated silver amount 0.4 Gelatin 0
．． 8ExS-1 (sensitizing dye) 4.0xlO-'E
xS-2 (enhancing pigment) 0. lX10-'ExS-
5 (sensitizing dye) 6.5X10-'ExS-7 (sensitizing dye) 6.5X10-'ExC-1 (cyan coupler) 0.17ExC-2 (cyan coupler) 0.05ExC-3 (magenta colored cyan coupler) ) 0.09 3rd Calendar (
Medium-sensitivity red-sensitive emulsion layer) Iodide 1m emulsion (Ag 16 mol%, core-shell ratio 2:
1 internal height Agl, equivalent sphere diameter 0.65 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.55 silver iodobromide emulsion (Ag 14 mol 1) Uniform Agl type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 3
7%, spherical particles, diameter/thickness ratio 3.0) Application 1! Amount 0. 1 Gelatin 1. 0ExS-1
(Sensitizing dye) 5.0X10-'ExS-2 (enhancing dye) 0.2X10-'ExS-5 (sensitizing dye)
8.2X10-'ExS-7 (enhancing pigment)
8.2X10-'ExC-1 (cyan coupler)
0.31ExC-2 (cyan coupler) 0.
01ExC-3 (Magenta colored cyan coupler) 0.09 4th layer (
High-sensitivity red-sensitive emulsion J1) Silver iodobromide emulsion (Ag 16 mol%, internal high Agl type with core-shell ratio 2:1, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/ Thickness ratio 2.5) Coated silver 110.9 Gelatin 0. 8
ExS-1 (sensitizing dye) 6.4X10-'ExS
-2 (sensitizing dye) 0.9XIO-'ExS-5 (
Sensitizing dye) 10.4X10-'ExS-7 (sensitizing dye>10.4X10-'ExC-1 (cyan coupler) 0.07ExC-4 (cyan coupler) 0.08Solv-1 (solvent)
0.07 Solv-2 (solvent), 0.07 Solv-3 (solvent) 0.020 pd-
7 (Antifoggant) 4,6X10-"5th layer (middle N) Gelatin 0.6UV-4 (
Ultraviolet absorber "J O,03UV-5 (ultraviolet absorber) 0.0.4Cpd-1 (color mixing prevention agent) 0.1 Polyethyl acrylate latex 0.08Solv-1
(Solvent) 0.05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion Ag 14 mol% uniform type. Equivalent ball diameter 0.4μ
, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 37%, plate-shaped particles, diameter/thickness ratio 2°0 Coated silver amount
0.18 Gelatin 0. 4
ExS-3 (sensitizing dye) 2X10-'ExS
-4 (sensitizing dye) 7X10-'ExS~5(
Sensitizing dye) lXl0-'ExM-5 (magenta coupler) 0.11ExM-7 (yellow colored magenta coupler) 0.03ExY-
8 (DIR coupler) 0.01Solv-1 (solvent) 0.09Solv-4 (solvent)
0.01 7th layer (medium-sensitivity green-sensitive emulsion N) Silver iodobromide emulsion (Ag 14 mol%, surface height Agl type with core-shell ratio 1:1, equivalent sphere diameter, equivalent sphere diameter 0.5μ, equivalent sphere diameter Coefficient of variation 20%, plate-like particles, diameter/thickness ratio 4.0) Coated silver amount 0.27 0.6 2X10-'7X10-'lXl0-' 417 Gelatin ExS-3 (sensitizing dye) ExS-4 (sensitizing dye) Sensitive dye) ExS-5 (enhancing dye) ExM-5 (magenta coupler) ExM-7 (yellow colored magenta coupler) ExY-8 (DIR coupler) Solv-1 (solvent) Solv-4 (?8 agent) 8th layer (High-sensitivity green-sensitive emulsion N) Silver iodobromide emulsion (A″g1B.

0, 04 0, 02 0, 14 0, 02 7 mol%, multilayer structure particles with a silver content ratio of 3:4;2, Agr content of 24 mol from the inside, 0 mol%, 3 mol%, equivalent sphere diameter 0. 7 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 1.6) Coated silver amount 0.7 0.8 2X10-'lXl0-'3X10-' 0, 1 Gelatin ExS-4 (increased Sensitizing dye) 5゜EMS-5 (Sensitizing dye) ExS-8 (Sensitizing dye) 0゜ExM-5 (Magenta coupler) ExM-6 (Yellow colored magenta coupler) ExY-8 (DIR coupler) ExC-1 ( Cyan coupler) ExC-4, (cyan coupler) Solv-1 (solvent) Solv-2 (solvent) Solv-4 (solvent) Cpd-7 (antifoggant) 9th layer (middle N) 0, 03 0, 02 0,02 0.01 0,25 0,06 0,01 1XIO-' Gelatin 0. 3Cpd-1
(Color mixing prevention agent) 0.04 Polyethyl acrylate latex 0.12 Solv-1
(Solvent) 0.02 1st O layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag+6 mol%, internal high Agl type with core-shell ratio 2:1, equivalent sphere diameter 0
．． 7μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particle, diameter/
Il ratio 2.0) Coated tlffi 0.68 silver iodobromide emulsion (Ag 14 mol%, uniform type sphere equivalent diameter variation coefficient 37%, plate-like grains, diameter/thickness ratio 3.0) Coated silver itO, 19 gelatin 1.
0ExS-3 (sensitizing dye) 6xlO-'Ex
M-10 (DIR coupler) 0.19Solv-1 (solvent) 0.20Solv-3 (solvent)
0.05 11th layer (yellow filter layer) Yellow colloidal silver 0.06 Gelatin 0.8 Cpd-2 (yellow dye) 0.13 Solv-1 (I agent)
0.13Cpd-1 (color mixing prevention agent)
0.07Cpd-6 (antifoggant) 0.0
02H-1 (Hardening agent) 0.13 1st
2N (Low-sensitivity blue-sensitive emulsion N) Silver iodobromide emulsion (Ag 14.5 mol%, uniform-Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Amount per application 0,
5 Silver iodobromide emulsion (Al 13 mol%, uniform-Agl type, equivalent sphere diameter 3.0μ, coefficient of variation of equivalent sphere diameter 30%, plate-like grains,
Diameter/thickness ratio 7.0) Coating i Length i 0.25 Gelatin 1.8ExS-6 (
Exacerbating dye) 9XIO-'ExC-1 (cyan coupler) 0.06ExC-4 (cyan coupler) 0,03ExY-9 (DIR coupler)
0.14ExY-1i (yellow coupler) C1
, 89S olv-1 (? Yo fl)
0.42 13th layer (middle layer) Gelatin 0.7ExY-12
(DIR Coupler) 0.20Solv-1 (I)
0.34 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag I I Q mol%, internal high AgI
Type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, multiple twinned plate-like particles, diameter/rg-ratio 2.0)
Coated silver amount 0.5 gelatin
0. 5ExS-6 (exacerbation pigment) xxt
o-4ExY-9 (DIR coupler) 0.01E
xY-11 (yellow coupler) 0.20ExC-1 (
Cyan coupler 1 0. Q2SOIV-1 (?8 agent) 0.10 15th layer (1st
Protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform Agl type, equivalent sphere diameter 0.07μ) Coated silver amount 0.12 Gelatin 0.9UV-4 (ultraviolet absorber) 0.11UV-5 (ultraviolet absorber) (solvent) 0.16Solv-5 (solvent)
0.02H-1 (hardener),
0.13Cpd-5 (scavenger) O,,
10 Polyethyl acrylate latex 0.09 16th layer (second protective layer) Fine grain silver bromide emulsion (Ag 12 mol%, uniform-Agl type, equivalent sphere diameter 0.07μ) Coated silver amount 0.36 Gelatin 0.55 Poly Methyl methacrylate particles 1.5μ in diameter 0.2H-1 (hardener) 0.17 In addition to the above ingredients, each layer contains emulsion stabilizer Cpd-3 (0.07g/po) and surfactant Cpd. -4 (0.03 g/rrr) was added as a coating aid.

V H C) 1° C11s　C(:l+3 l13 V H 113CCC113 113 113CCCH3 Cl□ UV-4 C113 CH3 +CO, -C±1 +CHz-C+y 0 Co-0-CH3 N UV-5 xF-1 olv-2 C 啼H1 啼 olv-4 C.I.

CH.

olv-5 pd 2 pd p d-6 N = N pd-9 (i) Cal-1,0 COCHz (i) CsHlqOCOCHS OiN apd-8 p d-5 Hff p d 0 Cs F + q S 02 N (Cx Hq)
CHt COOK (Preparation of Sample 602) The 1N black colloidal silver of Sample 601 was replaced with a fine particle dispersion of Compound 1-2 of the present invention (0.2 g/n(). Compound 1-2 of the present invention Dispersion No. 2 was prepared by the following method.

Water (21,7,7) and sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonic acid 3-5 in 5% aqueous solution
% aqueous solution of p-octylphenoxy poly(degree of polymerization 10)
0.5 g of oxyethylene ether was placed in a 700-pot mill, and 1. OOg and 500 ml of zirconium oxide beads (1 m diameter) were added and the contents were dispersed in a vibrating ball mill for 8 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 Compound 1-2 of the present invention.

(Preparation of Sample 603) Sample 602 was prepared in the same manner as Sample 602, except that Compound 1-4 of the present invention was used instead of Compound 1-2 of the present invention.

(Preparation of sample 6040) In sample 602, compound 1-4 of the present invention (0.1 g/rrf) and 1-2 were used instead of compound 1-2 of the present invention.
Sample 602 was prepared in the same manner as sample 602 except that 21 (0.1 g/rrf) was used at the same time.

(Preparation of Sample 605) In Sample 602, the following Comparative Compound 6-1 (compound described in JP-A-52-92716) (0.2 g/rl'?) was used instead of Compound 1-2 of the present invention. It was produced in the same manner as sample 602 except that sample 602 was used.

Comparative Compound 6-1 After exposing the samples 601 to 605 obtained as above, they were treated according to the method described in Table 7.

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

Raw color image (unit: g) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene = 1.1-Diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide 1.0 Hydroxylamine sulfur M1 4-[N-Ethyl-N-( β-Hydroxyethyl)aminoco-2-methylaniline sulfate solution was added to pH. Add 2.4 4.5 1.1! to, 05 (unit g) 120.0 10, 0 100, 0 10, 0 0.005 mole 15, Qm t, 01 pH 6,3 Reduction lsu 1 tau (unit g) Ethylenediaminetetraacetic acid ferric ammonium di Water salt 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 wt aqueous ammonia (27%) 6. Add od water
1,0N pH 7,2 A hotbed column filled with tap water washed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas) Water was passed through the water to reduce the concentration of calcium and magnesium ions to 3 mg/l or less, and then sodium dichloride isocyanurate was added at 20 mg/j! and 0.15 g/2 sodium sulfate were added. The pH of this solution is 6
．． It is in the range of 57.5.

Stable blood (unit: g) Formalin (37%) 2. 0dd Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water
1.0IPH5.0-8.0 The obtained sample was subjected to sensitometry, and the results shown in Table 8 were obtained.

By 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 with no decrease in sensitivity, no fogging, no residual color after processing, and a small amount of residual silver.

Example 7 Preparation of Sample 701 A multilayer color light-sensitive material consisting of each layer having the following composition was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm, and designated as Sample 701. The numbers represent the amount added per bottle. Note that the effects of the added compound are not limited to the described uses.

1st layer: Antihalation layer Black colloidal silver 0.25g Gelatin 1.9g Ultraviolet absorber U-
10,04g Ultraviolet absorber U-20,1g Ultraviolet absorber U-30,ig Ultraviolet absorber U-60,1g High boiling point solvent Oi1-10.1g 2nd layer: Intermediate layer gelatin 0.40g Compound C
pd-D Long high boiling point organic solvent 0
il-340 ■ 3rd layer: Fine grain silver iodobromide emulsion covered with intermediate layer (average grain size 0.06μ, Agl content 1 mol%) Silver amount
0.05g gelatin 0.4g 4th layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.4μ, Agl content 4゜5) Mol% monodisperse cubic and average particle size 0.3μ, Agl content 4.5mol%
1:1 P mixture of monodisperse cubes) silver content 0
．． 4g Gelatin 0.8g Coupler C-10.20g Coupler C-90.05g High-boiling organic solvent 0i1-10.1g 5th layer: Medium-sensitivity red-light emulsion layer Spectral enhancement with sensitizing dyes S-1 and S-2 Sensitized silver iodobromide emulsion (monodisperse cubic with average grain size 0.5μ, Agl content 4 mol%) iiit 0.4g gelatin 0.8g coupler C
-10,2g Coupler C-20,05g Coupler C-30,2g High-boiling point organic solvent 0il-10,,1g 6th layer: High red light emulsion layer Spectroscopy with sensitizing dyes S-1 and S-2 Sensitized silver iodobromide emulsion (monodisperse twinned grains with average grain size 0.7μ and Agl content 2 mol%) Silver amount 0.4g Gelatin 1.1g Coupler C
-30.7g Coupler C-10.3g 7th layer: Intermediate layer gelatin 0.6g Dye D-1
0.02g 8th layer: Silver iodobromide emulsion covered with intermediate layer (average grain size 0.06μ, Agl
Content: 0.3 mol%) Gelatin 1.0 g Color mixing inhibitor Cpd-A 0.2 g 9th layer: Low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with enhancing dyes S-3 and S-4 (average A 1:1 mixture of monodisperse cubes with a grain size of 0.4 μ and an Agl content of 4°5 mol % and monodisperse cubes with an average grain size of 0.2 μ and an Agl content of 14.5 mol %) Silver amount 0.
5g Gelatin 0.5g Coupler C-40, 10g Coupler C-70, 10g Coupler C-80, 10g Compound Cpd-B O, 03g Compound Cpd-E O, Ig Compound CPd-
FO, Ig compound cpa-c
o, Ig compound CPd-HO, 1g 10th layer: Medium-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size 0.5μ, AgT content 3 Mole% monodisperse cubic) Silver amount 0.4g gelatin
0.6g Coupler C-40, Ig Coupler C-70, 1g Coupler C-80, 1g Compound Cpd-B O, 03g Compound Cpd-E 0.1g Compound Cpd-F 0.1g Compound Cpd-G O, 05g Compound Cpd- HO, 05g High-boiling organic solvent 0il-10,01g 11th layer: High-sensitivity green malignant emulsion layer Silver iodobromide emulsion spectrally enhanced with sensitizing dyes S-3 and S-4 (average grain size when converted to spheres: 0°) 6μ, Agl content 1.3 mol%
, 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 Compound Cpd-80,08g Compound Cpd-E O,Ig Compound C
pd-FO, Ig compound Cpd-G
O, 1g Compound Cpd-HO, 1g 12th layer: Intermediate layer gelatin 0.6g Dye D-2
° 0.05g 13th layer: yellow filter layer yellow colloid silver amount 0.1g gelatin
1.1g color mixing prevention agent Cpd-A
O, 01g 14th N: Intermediate layer gelatin 0.6g 15th layer:
Low-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
A 1:l mixture of monodisperse cubes with an average particle size of 0.4 μ and an Ag+ content of 3 mol % and monodisperse cubes with an average particle size of 0.2 μ and an Ag content of 3 mol %) Silver amount 0.6 g
Gelatin 0.8g coupler C
-50.6g 16th layer: Medium-speed blue-sensitive emulsion layer Silver iodobromide emulsion enhanced with sensitizing dyes S-5 and S-6 (
Average particle size 0.5μ, Ag! Monodispersed cubes with a content of 2 mol%) Silver amount 0.4 g gelatin
0.9g Coupler C-50, 3g Coupler C-60, 3g 17th layer: High sensitivity front window emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Average particle diameter when converted into spheres: 0. 7μ, Agl content 1.5 mol%
, tabular grains with an average diameter/thickness of 7) Silver content: 0.4 g Gelatin 1.
2g coupler C-60, 7g 18th layer: 1st protective layer gelatin UV absorber U-1 UV absorber U-3 UV absorber U-4 UV absorber U~5 UV absorber U-6 Formalin scavenger pd-C Dye D-3 19th layer: Fine grain silver iodobromide emulsion covered with second protective layer (average grain size 0°06μ
, Ag + content 1 mol%) Silver amount 0, 8g 0.1g g 4g 3g 3g 5g 5g 0.05g Gelatin 0, 4g 20th layer: 3rd protective layer gelatin 0.4g polymethyl methacrylate (average particle size 1.5μ ) 0.1g 4:6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5μ) 0.1g silicone oil
0.03g Surfactant W-13°0■ In addition to the above composition, gelatin hardener H1 and a coating and emulsifying surfactant were added to each layer.

In addition, in the emulsion used here, monodisperse means that the coefficient of variation is 20% or less.

-1 0■ -2 H -3 0■ -4 +C11□-C1l+Goko=--1-÷CIl□-C1
++. ,.

-7 CI! .

1, -8 Oil 1 Dibutyl phthalate Oil 2 Tricresyl phosphate pd-A H pd-H -4 ■0 pd-D 11 pd-G -5 -1 -2 -3 D-1 (C1b) 3S03゜(CHz ) 5sOs8HN (CJs) sC! H5 C, HS -2 SO3'HN (C2H5, 503""0sNa -1 CHz = CHS Ot CHt CON HCHz
CHt=CH3O□CHz CON HCHtCI+3 (Preparation of Sample 702) In Sample 701, the yellow colloid in the 13th layer was replaced with a fine particle dispersion of Compound 1-19 of the present invention (0.2 g/rrr). The l-19 fine particle dispersion was prepared in the same manner as the r-2 fine particle dispersion in sample 602 in Example 6.

(Preparation of sample 703) Sample 702 was prepared in the same manner as sample 702, except that compound l-24 of the present invention was used instead of l-19.

(Preparation of Sample 704) Sample 702 was prepared in the same manner as Sample 702, except that Compound 1-25 of the present invention was used instead of 1-19.

After exposing the samples 701 to 704 obtained as above, they were processed in the following manner.

−Physical process Process Time Temperature First development 6 minutes 38°C Wash with water 2 minutes Reversal 2 minutes Color development 6 minutes Adjustment 2 minutes Bleached white 6 minutes Fixed arrival time: 4 minutes Wash with water 4 minutes Safe, steady, 1 minute, constant Rolling dry The following composition of the treatment liquid was used.

Nisato 1 Wataru Water 70〇-Nitrilo-N,N,N-1-rimethylenephosphonic acid pentasodium salt Sodium sulfite Hydroquinone monosulfonate Sodium carbonate (-hydrate) 1-Phenyl-4 methyl-4 - Hydroxymethyl-3-pyrazolidone Potassium bromide Potassium thiocyanate Potassium Iodine (0.1% 7 volumes) 1 tin (trihydrate) g 0g 0g 0g g 2,5g 1,2g - 1000+d 70 〇- p-Aminophenol Sodium hydroxide Add glacial acetic acid water and add light and water nitrilo-N,N,N- Trimethylenephosphonic acid pentasodium salt Sodium sulfite Sodium triphosphate (12 hydrate) Potassium bromide Potassium iodide (0.1% solution) Sodium hydroxide Citrazate N-ethyl-N-(β-methanesulfone (amidoethyl) -3-methyl-4-aminoaniline sulfate 0.1g g 5- 000ml 00ad 6g g 0ml g 1,5g 1g 3.6-cythiaoctane-1゜8-diol Add water and straighten the dish to water sulfite Sodium ethylenediaminetetraacetate (trihydrate) Add thioglycerin glacial acetic acid water and add concentrated sodium ethylenediaminetetraacetate (trihydrate) Ammonium ethylenediaminetetraacetate iron(III) (trihydrate) Potassium bromide water g 000m1 70〇-2g go, 4--1000d 80〇-g 20g 00g 100(ld constant jL.

Water BOOm
l Thiolium 1,000 sulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water
10100O! Regular water sprinkling 800-
Formalin (37% by weight) 5. Omj! Fuji Drywell (surfactant manufactured by Fuji Film ■) 5.0 ml of water was added to 1000 ral.The obtained sample was subjected to sensitometry, and the results shown in Table 9 were obtained. However, in Table 9, the values of residual W& amount are the results of processing with the bleaching time shortened to 2 minutes.

Table 9 shows the sensitivity of the blue-sensitive layer when exposed after 3 days of aging)
- (Sensitivity of blue-sensitive layer before aging) rate *) D: 45°C, 80
Glue when exposed to light after aging at %RH for 3 days.

When the compound of the present invention is used as a yellow filter, a color photographic 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. Also, blue rf based on yellow colloidal silver! ! It can be seen that a color photographic material with a high D can be obtained because there is no fogging of the layers.

Example 8 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic light-sensitive material was prepared by coating the next 4th layer to the next 4th layer on the front side of the film (0 micron), and the 6th layer to the 5th 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 Lll, al
The values were 88.0, -0.20, and -0.75 for l and be systems. ).

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

The emulsion used in each layer was prepared according to the manufacturing method of Emulsion M1. However, Lippmann emulsion, which does not cause surface chemical aggravation, was used for the four-layer emulsion.

11'! (Antihalation layer) Black colloidal silver 0.10 gelatin
0.70 2nd layer (intermediate layer) Gelatin 0.70 31st (low sensitivity red sensitivity N) Silver bromide (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 1.0
0 cyan coupler (ExC-1, 2, 3 tit: 0.
2) 0. 30 anti-fading agent (
Cpd-1, 2, 3, 4 equivalent) 0.18 Stin inhibitor (Cpd-5) 0.003 Force puller dispersion medium (Cpd~6) 0.03 Coupler solvent (Solv-1, 2, 3, etc.) '!i) 0.12 4th layer (high sensitivity red sensitive layer) Silver bromide spectrally sensitized with red enhancing dyes (ExS-1, 2, 3) (average particle size 0.60μ, size distribution 15%)
, octahedron] 0.14 gelatin
1.00 Cyan coupler (ExC-1,2,3 l:l:0.2) 0.30 Antifading agent (CPd-1,2,3,4 etc. M) 0.18 Coupler dispersion medium (Cpd- 6) 0.03 coupler solvent (Solv-1, 2, 3 equivalent) 0.12 5th layer (middle N) Gelatin color mixing inhibitor (Cpd-7) Color mixing inhibitor solvent (Solv-4, ■, 00 0 , 08 5 equivalents) 0, 16 Polymer Latinx (Cpd-8) 0.10 6th layer (low sensitivity green sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4)
Average particle size 0.25μ, size distribution 8%, octahedral)
0.04 Silver chlorobromide spectrally sensitized with green brightening dye (ExS-4) (5 mol% silver chloride, average grain size 0.40 μ, size distribution 10%, octahedral) 0.06 Gelatin 0. 80 Magenta Coupler (ExM-1,2,3 eq.) 0, 11 Anti-Fade Agent (Cpd-9, 26 etc. U O015 Anti-Stain Agent (cpct-to, 11.12.13 to 10 Nia: 7:1 ratio) 0.025 force puller dispersion medium (C
pd-6) 0.05 coupler solvent (Solv-4
, 6 etc. 0, 15 7th layer (high sensitivity green sensitive layer) Silver bromide (
Average particle size 0.65μ, size distribution 16%, octahedral) 0.10 gelatin
0.80 Magenta coupler (ExM-1, 2, 3 equivalent) 0.11 Anti-fading agent (Cpd-9, 26 equivalent) 0.15 Anti-stinting agent (Cpd-10, 11, 12, 13 in 1
0 near:7:1 ratio) 0.025 force puller dispersion medium (Cp
d-6) 0.05 coupler solvent (Solv-4,
6 equivalents) 0, 15 81'll (middle N) 9th layer (yellow filter layer) same as the 5th layer Yellow colloid S gelatin color mixing inhibitor (Cpd-7) Color mixing inhibitor solvent (Solv-4, Polymer latex 0, 12 0, 07 0, 03 5 equivalents) 0.10 0.07 (Cpd-8) 10th stone (intermediate N) 11th layer same as 5th layer (low-range blue sensitive layer) Blue Silver bromide spectrally sensitized with sensitizing dye (ExS-5,6) (average grain size 0.40μ, size distribution 8%, octahedral) 0.07 blue sensitizing dye (ExS-5,6)
) spectrally sensitized silver chlorobromide (silver chloride 8 mol %, average grain size 0.60 μ, size distribution 11%, octahedral) 0.
14 Gelatin 0.80 Yellow coupler (ExY-1,2 etc. M) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-staining agent (Cpd-5,15 in a 1=5 ratio)
0.007 force blur dispersion medium (CPd-
6) 0.05 coupler solvent (Solv--2)
0.10 12th layer (high sensitivity blue sensitive layer) Spectral sensitization 85μ with blue sensitizing dye (ExS-5,6),
Silver bromide (average grain size O.

gelatin yellow coupler (ExY-1, anti-fading agent (Cpd-14) anti-stinting agent (Cpd-5, with) coupler dispersion medium (CPd-6) coupler dispersion medium (Solv-2) 13th layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber 1,00 (Cpd-2,4,16 equivalent) 0,50 Color mixing inhibitor, (Cpd-7,17 equivalent) 0,03 Dispersion medium (Cpd- 6) 0.02 UV absorber solvent (Solv-2, 7 equivalent) 0.08 Anti-irradiation dye (Cpd-18, l9.20
(in a ratio of 10:13:2o) 0.05 14th layer (protection N) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1
μ) 0.03 Acrylic modified copolymer of polyvinyl alcohol 0,Ol Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
0.05 gelatin
1.80 gelatin hardener (H-1, H-2 equivalent) 0.
18 15th layer (back layer) Gelatin 2.50 UV absorber (Cpd-2, 4, 16 equivalent) 0, 50 16th layer (back protective layer) Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5 tln etc. 1
0.05 gelatin
2. OO gelatin hardener (H-
1, H-2 equivalent) 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 with vigorous stirring at 75°C over 15 minutes.
Octahedral silver bromide grains with an average grain size of 0.40 μm 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 7111 g of chloroauric acid (tetrahydrate) were added in sequence.
Chemical sensitization treatment was performed by heating at °C for 80 minutes. Using the particles obtained in this way as cores, they were further grown in the same precipitation environment as the first time, and the final average particle size was 0.7.
The octahedral monodisperse core/shell silver bromide emulsion of μ was obtained with a coefficient of variation of 0 grain size of about 10%. This emulsion has SR
1.5 μm of sodium thiosulfate per mole and 1. 5
A chemical sensitization treatment was carried out by adding chloroauric acid (tetrahydrate) and heating at 60°C for 60 minutes to obtain an internal latent image type silver halide emulsion.

Each photosensitive layer contains ExZK-1 and ExZK- as nucleating agents.
2 to 10-'104% by weight of silver halide, respectively.
CP d-22 was used at 104% as a nucleation accelerator. Furthermore, each layer contains alkanol X as an emulsification and dispersion aid.
C (Dupon) and sodium alkylbenzenesulfonate, succinate ester and Ma as coating aids.
gefac F-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 Nα801.

In sample 801, the ninth layer of yellow colloidal silver was replaced with compound l-19 of the present invention prepared in the same manner as in Example 7.
The sample replaced with a fine particle dispersion of 0.2 g/bo) was designated as sample Nα802.

A sample obtained by replacing compound 1-19 with l-24 in sample 802 was designated as sample Nα803.

A sample obtained by replacing compound l-19 with l-25 in sample 802 was designated as sample Nα804.

The compounds used in this example are shown below.

(CHHz)s (CHz)i OzNa ExS-5 ExS pct-s H H CPd-6 CPd-7 0■ 11 P a-s +CH, -CHsu1 COOC2H.

CPd ] 10 CPd Pd-3 CPd CPd-10 CPd-L l pd 12 pd-13 0] 1 11 pd-14 pd-15 H pd 9 pd 0 C1l□C00K pd to C112COO 2 pd-23 pd-24 pd 6 pd-17 H 11 pd 8 S (Stl in h, K pd-25 Stl pct 6 xC-1 l xC-2 H ExC ExM-3 Hi ExM-1 xY-1 Cρ ExM xY-2 "Q olv-1 ol -2 ol -3 olv-4 olv-5 olv-6 olv-7 -1 -2 ExZK-1 Di(2-ethylhexyl) sebaket trinonyl phosphate di(3-methylhexyl) phthalate 1 monotricresyl phosphate dibutyl Phthalate trioctyl phosphate di(2-ethylhexyl)phthalate 1-bis(vinylsulfonylacetamido)ethane 46-dichloro-2-hydroxy-1,3,51 riazine Na salt 7-(3-ethoxythiocarbonylamino benzamide)-9-methyl-10-prohagi-1,2゜34-tetrahydroacridinylam trifluoromethanesulfonateExZK-22-(4-f3- (3-13-(5-(
3-(2-chloro-5(1-dodecyloxycarbonylethoxycarbonyl)phenylrubamoyl]-4-hydroxy1-naphthylthio)tetrazol1-yl]phenyl)ureido]benzenesulfonamido)phenyl)-1-formylhydra After imagewise exposing the silver halide color photographic window optical materials 801 to 804 prepared as described above, the cumulative replenishment amount of the solution is determined by the method described below using an automatic processor. Continuous treatment was carried out until the amount increased to three times the amount.

Color development 135 seconds 38°C15 low 300IR1
/ Po bleach fixing 40〃33〃3〃300〃Washing (1)
40〃33〃3〃 Washing (2) 40〃33〃3〃320 The method of replenishing the washing water is to refill the washing bath (2) and
A so-called countercurrent replenishment system was adopted in which the overflow liquid of 2) was led to the washing bath (1). At this time, the amount of bleach-fix solution brought into the washing bath (1) from the bleach-fix bath for photosensitive materials is 3
5 ad/n (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.

Seishori Mioka Mother Liquor Replenisher D-Sorbit Sodium Naphthalene Sulfonate/Formalin Condensate Ethylene Diamine Tetraacetic acid Lakis Methylene Phosphonate Diethylene Glycol Benzyl Alcohol Potassium Bromide 0.15 g 0.20 g 0,15 g 0.20 g 1. 5g 1.5g 12.0d 16.0ad 13.5M118.0M1 O, 80g Henctriazole sodium sulfite N,N-bis(carboxymethyl)hydrazine D-glucose triethanolamine N-ethyl-N-(β methanesulfonamidoethyl )-3 Methyl-4-aminoaniline sulfate potassium carbonate optical brightener (diaminostilbene type) 0.003g 0.004g 2.4g 3.2g 6.0g 8.0g 2.0g 2.4g 6.0g 8 .0g 6.4g 8.5g 30.0g 25.0g 1.0g 1.2g pH (25°C) 10.25 10.75 Ethylenediamine 4-acetic acid mother solution Same acid as replenisher mother solution・Disodium・Dihydrate ethylenediaminetetraacetic acid・Fe(I[I)・Ammonium・Dihydrate ammonium thiosulfate (700g/1) Sodium p-toluenesulfinate Sodium bisulfite 5-mercapto-1°34-triacetic acid 4. 0g 70.0g 180s+j 20.0g 20°Og 0.5g Ammonium nitrate 10.0gIR-400
) to reduce the concentration of calcium and magnesium ions to below 3 ■/l, followed by sodium dichloride isocyanurate 20 ■/l! , and 1.5 g/l of sodium sulfate were added. The pH of this solution was in the range of 6.5-7.5.

On the other hand, before imagewise exposing samples 801 to 804,
After leaving it for 3 days with C155% RF, it was exposed to imagewise light and subjected to the same treatment.

The results are shown in Table 10.

Table 10 pH (25° (:) 6.20 Iceberg water Both the mother liquor and the replenisher were tap water, H-type strongly acidic cation exchange resin (Amberlite JR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin ( Same amber light *) Dmin: (4
Dmin when exposed after aging at 5°C and 55% RH for 3 days (D+win before aging) By using the compound of the present invention, it is possible to obtain a color photographic material with a change in Dmin over time with less procedural amendments. I feel angry.

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a hydrophilic colloid layer containing a solid fine particle dispersion of a dye represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 each represent an alkyl group, alkenyl group, or aryl group, R_3 and R_4 each represent a hydrogen atom or a monovalent group, and Z_1 , Z_2 each represent a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocycle, and L is a methine group or 3, 5, or 7 methine groups connected by a conjugated double bond. It represents the resulting linking group, X^- represents an anion, and l_1 and l_2 each represent 0 or 1.