JPH01537A - Silver halide color photographic material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to silver halide color photographic materials, and more specifically, the stability of photographic sensitivity during manufacturing and storage, and the stability of color images after processing. This invention relates to a silver halide color photographic material with excellent stability.

(Prior art) Dye images of silver halide color photographic light-sensitive materials are sometimes stored by being exposed to light for long periods of time, and sometimes stored in dark places for long periods of time. It is also known that the color may fade significantly depending on the condition of storage determined by heat, humidity, oxygen, etc. In general, fading in the former case is called photobleaching, and fading in the latter case is called dark fading, and when color photographic materials are processed and stored as recording media for a long period of time, such photofading and dark fading are required. It is desirable to maintain a balance in the degree of fading of yellow, magenta, and cyan dye images while minimizing the degree of fading, that is, by increasing light fastness and dark fastness. However, the degree of photobleaching and dark fading of yellow, magenta, and cyan dye images differs among these dye images, and after long-term storage, the overall color balance of the three colors will be disrupted. There was a problem in that the image quality in terms of color reproduction and gradation reproduction deteriorated.

The degree of photobleaching and dark fading varies depending on the coupler used and various other factors, but in the case of dyes used in many conventional color photographic materials, in terms of dark fading, yellow is second only to cyan dye images. It is known that fading is more likely to occur in the order of dye images and magenta dye images, and in particular, the degree of dark fading in cyan dye images is greater than in other dye images.

Therefore, in order to maintain good color balance over a long period of time when the three colors yellow, magenta, and cyan fade, it is necessary to suppress dark fading of the cyan dye image as much as possible. Various attempts have been made to improve discoloration and dark fading. Such efforts can be broadly divided into two areas: one is the development of new couplers that form dye images with low fading resistance, and the other is the development of new additives that prevent color fading. It is to develop.

Many phenolic cyan couplers that form cyan dyes have been known in the past. For example, U.S. Patent No. 2.8
2-[α-2,4-ditertiary amylphenoxybutanamide)-4,6- described in No. 01.171
It is known that dichloro-5-methylphenol has the disadvantage that the coloring dye formed therefrom has good light resistance but poor heat resistance.

Furthermore, couplers in which the 3- or 5-position of the phenol is substituted with an alkyl group having 2 or more carbon atoms, for example,
9-11572, JP-A-60-209735, JP-A-60-205447, etc. Although the dark fastness of cyan images produced from these couplers is improved to some extent, they are not only insufficient, but are also known to have poorer photobleaching properties than the cyan couplers mentioned above.

In addition, 2,5-diacylaminophenol cyan couplers in which the 2- and 5-positions of phenol are substituted with acylamino groups are available, for example, in U.S. Pat. , No. 895.826,
It is described in JP-A-50-112038, JP-A-53-109630, and JP-A-55-163537. These 2
．． The 5-diacyl aminophenol coupler has very good dark fastness of the cyan image formed, but the light fastness of the cyan image formed is even worse than the former two cyan couplers, and it is also difficult to use as a photosensitive material for printing. When used, the disadvantage is that the hue tends toward shorter wavelengths. In order to compensate for this drawback, it has been used in combination with the former two cyan couplers, but it has been found that the dark fastness is considerably reduced.

The 1-hydroxy-2-natsutamide type cyan coupler is
Lightfastness is generally insufficient.

In addition, the 1-hydroxy-2-acylaminocarbostyryl cyan coupler described in JP-A-56-104333 has good fastness to light and heat, but the spectral absorption characteristics of the color image formed are poor in color photography. It has been found that this is not preferable in terms of color reproduction, and that there are also problems such as pink stains being generated when irradiated with light.

Also, U.S. Patent No. 3.767.4125, JP-A-59-
Although the cyan polymer couplers described in Nos. 65844 and 61-39044 do have excellent dark fastness under low humidity conditions, they have the drawback of insufficient dark fastness under high temperature conditions. I found out what I was doing.

Additionally, in U.S. Patent No. 4,203,716, etc., a hydrophobic substance such as an oil-soluble coupler is dissolved in a water-miscible organic solvent, and this liquid is mixed with a loader pull polymer latex to load the hydrophobic substance into the polymer. A method is disclosed. However, the method using such a loader pull polymer latex has a problem in that the light fastness of cyan images in particular is inferior to the method using a high boiling point organic solvent that is immiscible with water. Furthermore, in order to sufficiently load the coupler and obtain a sufficient maximum color density, a large amount of polymer must be used, which has been found to have the disadvantage of increasing the cost and film thickness of photosensitive materials using it. Served. Japanese Patent Publication No. 48-30494 discloses that instead of using a high boiling point organic solvent, a hydrophobic heptad homopolymer with a specific structure or a hydrophilic monomer with a specific structure that is soluble in an organic solvent is used. There is a description that a photosensitive material containing an emulsified dispersion of a coupler using a copolymer with the above method has improved film quality, poor color restoration, photobleaching, storage stability before processing, etc.

However, when using a homopolymer of hydrophobic monomers as described above instead of a high-boiling organic solvent, there are problems such as low color development, the need to use a developing solution that does not contain nibenzyl alcohol, and emulsification. We have found that there are problems such as poor stability of the dispersion during storage. On the other hand, although the above-mentioned copolymers of hydrophobic monomers and hydrophilic monomers such as acrylic acid do improve the stability and coloring properties of emulsified dispersions slightly, they are completely insufficient. It has also been found that increasing the proportion of hydrophilic monomer in the copolymer causes a problem in that dark fastness deteriorates, especially under high temperature conditions.

Furthermore, in the case of Japanese Patent Publication No. 48-30494, a major problem was found that, especially when applied to cyan couplers, photobleaching was significantly worse than when emulsifying and dispersing with conventional high-boiling point organic solvents. .

(Problems to be Solved by the Present Invention) Thus far, couplers whose dark fastness has been improved by changing the coupler structure have been insufficient in terms of hue, color development, stain, or especially light fastness. There was a strong need for a new technology that could solve these problems at the same time.

On the other hand, benzyl alcohol has been widely used in the color development of silver halide color light-sensitive materials using conventional oil-protected couplers in order to improve color development and shorten processing time.

However, since benzyl alcohol has low water solubility, a solvent such as diethylene glycol, triethylene glycol or alkanolamine is required to facilitate dissolution. These compounds, including benzyl alcohol, have a large BOD value (biological oxygen demand) - COD (chemical oxygen demand) value, which indicates the environmental pollution load, and from the standpoint of environmental protection, these compounds should not be used. is preferred.

Furthermore, when benzyl alcohol is used, there is a disadvantage that it takes time for dissolution even if the above-mentioned solvents are used.

Furthermore, when benzyl alcohol is brought into the bleach bath or bleach-fixing bath, it tends to produce leuco forms of cyan dye, which causes a decrease in color density. Furthermore, since the washing-out speed of the developer components is delayed, the image storage stability of the processed photosensitive material may be adversely affected. Therefore, from these points as well, it is preferable not to use benzyl alcohol.

As described above, it has been desired to develop a coupler and an emulsified dispersion thereof that not only improves image storage stability but also has excellent color development even without the use of benzyl alcohol.

On the other hand, we have found that couplers or emulsified dispersions having excellent color image fastness as described above often exert effects on silver halide emulsions that affect photographic sensitivity.

That is, we found that the color enhancement sensitivity decreases when using the aforementioned phenolic cyan coupler, and that a similar decrease occurs when certain magenta couplers and yellow couplers are used. It is also desirable that techniques for improving sex do not produce such effects. The development of emulsion technology that is less susceptible to such effects is expected.

Therefore, the first object of the present invention is to form a silver halide dye image that has improved light fastness and dark fastness, and in particular can form a dye image that exhibits excellent color image storage stability even under high temperature and high humidity conditions. Our objective is to provide color photographic materials.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material which has a good fading color balance of yellow, magenta and cyan and whose color reproducibility does not deteriorate even after long-term storage.

A third object of the present invention is to create a dye image that does not adversely affect photographic characteristics, in particular does not reduce photographic sensitivity during the production or storage of light-sensitive materials, and has improved color image storage stability. An object of the present invention is to provide a silver halide color photographic light-sensitive material that can be formed.

A fourth object of the present invention is to exhibit sufficient color development even when processed with a color developing solution that does not substantially contain benzyl alcohol, and which is composed of a coupler emulsion dispersion with excellent stability and has excellent color image storage stability. An object of the present invention is to provide a silver halide color photographic light-sensitive material.

A fifth object of the present invention is to provide a silver halide color light-sensitive material in which the dark fastness of cyan dye images is improved without deteriorating the light fastness.

(Means for Solving the Problems) As a result of various studies, the present inventors have discovered that the above objectives can be achieved by the following silver halide color photographic light-sensitive material.

(1) On a support, at least one diffusion-resistant oil-soluble coupler that forms a dye by coupling with an acid form of an aromatic primary amine color developer, and a high-boiling organic solvent. In a silver halide color photographic material having at least one silver halide photographic emulsion layer containing an emulsified dispersion of lipophilic fine particles containing at least one kind, the emulsified dispersion of lipophilic fine particles contains the above coupler and a high boiling point. Obtained by emulsifying and dispersing a mixed solution in which at least one water-insoluble and organic solvent-soluble single or copolymer consisting of an organic solvent and at least one repeating unit having no acid group in the main chain or side chain coexists. The silver halide emulsion is a dispersion, and is characterized in that the silver halide emulsion consists of a monodisperse silver chloride, silver chlorobromide or silver bromide emulsion that is mainly surrounded by (100) planes and does not substantially contain silver iodide. A silver halide color photographic light-sensitive material.

(2) The silver halide color photographic material according to item (1), wherein the repeating unit having no acid group in the polymer has a 100-bond in its main chain or side chain.

3) The silver halide color photographic light-sensitive material according to item (2), wherein the repeating unit having no acid group of the polymer has a 1000-group in its main chain or side chain. .

(4) The repeating unit that does not have an acid group of the polymer has a -CON R, group in its side chain (however, R represents two substituents which may be the same or different, each of which is a hydrogen atom, substituted or unsubstituted). The silver halide color photographic light-sensitive material according to item (2), wherein the silver halide color photographic material has an alkyl group or an aryl group.

(5) The silver halide color photographic material according to any one of items (1) to (4), wherein at least one of the oil-soluble couplers is a phenolic cyan coupler.

(6) The silver halide color photographic light-sensitive material according to any one of items (1) to <4), wherein at least one of the oil-soluble couplers is a pyrazoloazole coupler.

(7) The silver halide color photographic material according to any one of items (1) to (6), wherein the silver halide emulsion is spectrally enhanced.

(8) Spectral enhancement dyes are monomethine and trimethine.

or pentamethine cyanine dye.

(9) The above-mentioned silver halide emulsion layer contains at least two types of the above-mentioned monodispersed silver halide emulsions, according to any one of items (1) to (8). silver halide color photographic material.

The present invention provides that desensitization of a silver halide emulsion caused by a dispersion obtained by emulsifying and dispersing a high-boiling organic solvent, a coupler, etc. in the presence of a surfactant is reduced by an emulsified dispersion containing such a polymer. This is based on the discovery that the above-mentioned desensitization and desensitization during storage of photosensitive materials after coating can cause crystallization of silver halide crystal grains only when a polymer is present. It was built horizontally based on the unpredictable fact that it is significantly reduced by habit.

In cases where the polymer, high-boiling organic solvent and coupler introduced into the emulsified dispersion have such an interaction with the silver halide emulsion and the color image fastness is improved by the polymer, certain silver halide emulsions It is completely unknown in the prior art, and it is difficult to predict, that the use of the same will bring about improvements in sensitivity and storage stability.

For example, the aforementioned US Pat. No. 4,203,716, which discloses latex dispersions, is silent on the specific requirements of such silver halide emulsions.

Also, Japanese Patent Publication No. 48-30 discloses polymer dispersion.
No. 494 also only describes preferred dispersants, but does not mention any requirements for preferred emulsions.

Furthermore, in the Examples of this patent specification, there is a description that a red-sensitive silver chlorobromide gelatin emulsion, a green-sensitive silver chlorobromide gelatin emulsion, and a blue-sensitive silver chlorobromide gelatin emulsion were used, but there are no more effective examples. There is no equivalent statement regarding the requirements. The results also show that coatings containing polymers do not affect the demonometric properties and that replacing a portion of the gelatin with a non-gelatin hydrophilic colloid binder increases the relative sensitivity of the coating. Although this is described, this is caused by differences in developer penetration, etc., and is different from the phenomenon involving color sensitization, which is the problem of the present invention. Moreover, nothing is mentioned here regarding the relationship with the specific spectral enhancer or the characteristics of the silver halide emulsion other than that it is silver chlorobromide.

Furthermore, JP-A-51-25133 and JP-A No. 60-140344
There is no specific description in No. 60-151636, etc.

In the above description, the term "acid group" refers to the remaining portion of an acid molecule after removing a hydrogen atom that can be converted into a metal, which forms the negative portion of a salt.

Further, repeating units that do not have an acid group include, for example, carboxylic acids, sulfonic acids, phenols having at least one electron-withdrawing group at the ortho or para position of the hydroxyl group, and naphthols having a pKa of about 10 or less. , means a repeating unit that does not contain active methylenes or their salts. Therefore, the coupler structure is considered an acid group here.

The diffusion-resistant oil-soluble coupler is
Cyan couplers represented by (II) or (II) are particularly preferred in the present invention.

General formula (1) General formula (n) H In the formula, R1, R4 and R5 each represent an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, and R2 is an aliphatic group. R3 and R6 each represent a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group. The aliphatic group herein refers to a linear, monobranched, or cyclic alkyl group, alkenyl group, or alkynyl group.

Further, R2 and R3 or R5 and R6 may be connected to each other to form a 5.6- or 7-membered ring to form a condensed ring such as carbostyryl or oxindole.

Furthermore, R1, R2, R3 or Yl, or R4, R5
, R6 or Y2 may form a dimer or more multimer 3.

Yl and Y2 represent a hydrogen atom or a group that can be separated after a coupling reaction with an oxidation product of a color developer.

The above-mentioned high boiling point organic solvent has the following general formula (m), (IV
), (V), (VI)-(■) or (■).

In the formula, Wl, Wl and W3 each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, and W4 is Wl
-0-Wl or 5-Wl, n is 1 to 5
is an integer up to and when n is 2 or more, W4 may be the same or different from each other, and in the -ffi formula (■),
Wl and Wl may be linked to each other to form a condensed ring.

W6 represents a substituted or unsubstituted alkyl group or aryl group, and the total number of carbon atoms constituting W6 is 12 or more.

After exposure, the silver halide color photographic light-sensitive material of the present invention has the following properties:
It is preferable to carry out development processing using a color developing solution that does not substantially contain benzyl alcohol.

Here, a color developing solution that does not substantially contain benzyl alcohol means that the concentration of benzyl alcohol in the developer is Q,
It means a color developing solution having a molecular weight of 5ce/12 or less. Preferably, the developing solution does not contain benzyl alcohol.

General formula (m) Wl Wl-0-P=0 General formula < ■) Wl -COOWl-Mountain (V
) W2/ 1-CON \ General formula (■) HO-W5 The present invention will be described in detail below.

The polymer used in the present invention may be any water-insoluble and organic solvent-soluble polymer consisting of at least one type of repeating unit that does not have an acid group in its main chain or side chain, but the repeating unit may be -C - A polymer having a bond is preferred in terms of color development and color image fastness. On the other hand, when a polymer consisting of a heptamer having an acid group is used, for example, as described in JP-A No. 55-65236, page 24 onwards, the effect of improving color image fastness is significantly reduced, so it is not preferable. Although it is often not, a small amount that does not significantly reduce the improvement effect,
You can use it. The polymer used in the present invention will be explained below by giving specific examples, but the polymer of the present invention is not limited thereto.

(A) Vinyl polymer Monomers forming the vinyl polymer of the present invention include acrylic esters, specifically methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and inbutyl acrylate. acrylate, 5ee-butyl acrylate,
tert-butyl acrylate, amyl acrylate,
Hexyl acrylate, coethylhexyl acrylate, octyl acrylate, tcrt-octyl acrylate 1. Co-chloroethyl acrylate, λ-bromoethyl acrylate, Hiro-chlorobutyl acrylate,
Cyanethyl acrylate, coacetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, cochlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrone rufuryl acrylate, phenyl acrylate,! -Hydroxypentyl acrylate, co,2-dimethyl-3
-hydroxypropyl acrylate, -monomethoxyethyl acrylate, 3-methoxybutyl acrylate, λ
-Ethoxyethyl acrylate, Co-propoxy acrylate, Cobutoki 7-ethyl acrylate), J
-(u-methoxyethoxy)ethyl acrylate, co(coptoxyethoxy)ethyl acrylate, ω-
Examples include methoxy7 polyethylene glycol acrylate (number of moles added 0 days?)/-i romocomet Φ diethyl acrylate, /,/-diethyl acrylate in dichloro-λ-ethane, and the like. In addition, polymers polymerized using the following mono i- can be used.

Methacrylic acid esters: Specific examples include methyl methacrylate and ethyl methacrylate.

n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, inbutyl methacrylate, 5ec-butyl methacrylate), tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, indyl methacrylate, chlorbenzyl methacrylate ,
Octyl methacrylate, stearyl methacrylate,
Sulfopropyl methacrylate, N-ethyl-N-7 ndyl aminoethyl methacrylate 1. z-(J-:yenylzorobiruo)ethyl methacrylate, dimethylaminophenol diethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, 7-enyl methacrylate, cresyl methacrylate,
Naphthyl methacrylate, λ-human tetraxyethyl methacrylate, ≠-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glyconyl monomethacrylate, comethoxyethyl methacrylate, 3-methoxybutyl methacrylate, λ
-7 Setoxyethyl methacrylate, Coacetoacetoxyethyl methacrylate, -1ethoxyethyl methacrylate, '-Z-iso-propoxyethyl methacrylate, Coptoxyethyl methacrylate, -1(
Comethoxyethoxy)ethyl methacrylate), -2-
(-monoethoxyethoxy)ethyl methacrylate, Co(coptoxyethoxy)ethyl methacrylate, ω-
Examples include methoxypolyethylene glycol methacrylate (number of moles added nt), allyl methacrylate, and dimethylaminoethyl methacrylate methyl chloride salt.

Vinyl esters: Specific examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caproate, vinyl chloroacetate, vinyl meth diacetate, vinyl phenyl acetate, vinyl benzoate, salicyl Acrylamides: For example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, human tetraxymethylacrylamide,
Methoxyethyl acrylamide, dimethylaminoblyacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoederacrylamide, N-(J-acetoacetoxyethyl)acrylamide, diacetone acrylamide, etc.: Methacrylamides: e.g. methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, te
rt-butylmethacrylamide, Schiffermethacrylamide, benzylmethacrylamide, dimethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, diethylacrylamide, diethylacrylamide, β-cyanethyl methacrylamide,
N-(Coacetoacetoxyethyl) methacrylamide, etc.; Olefins: For example, dicyclopentadiene, ethylene, flopylene, ty-thene, l-notene, vinyl chloride, vinylidene chloride, isoprene, chlorozolene, tutadiene, 2. Nisprenes such as 3-dimethylbutadiene, such as styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isoprobylstyrene, chloromethylstyrene, metoyacystyrene,
Acetoxystyrene, chlorstyrene, dichlorostyrene, bromustyrene, vinyl ammonium, methyl ester, etc.; vinyl ether rA:flLtt-j, methyl vinyl ether, phthyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, digeraminoethyl vinyl ether, etc. Other examples include puddel crotonate, hexyl heptaconate, dimethyl itaconate, dimethyl itaconate, diethyl maleate, dimethyl Yleate, zygdel maleate, diethyl hepmalate, dimethyl hepmalate, dibutyl hepmalate, Methyl vinyl ketone, 2-enyl vinyl ketone,
Methoxyether vinyl ketone, glycyl acrylate, glycyl acrylate, N-vinyloxazolidone.

Examples include N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, vinylidene cloide, methylenemalonitrile, and vinylidene.

The 7-mer used in the polymer of the present invention (for example, the above-mentioned 7-mer) can be used as a copolymer obtained by polymerizing two or more types, depending on the solubility improvement of the coupler. et al. used. In addition, to improve color development and solubility,
As long as the copolymer does not become water bathable, rR2! such as those listed below can be used as a comonomer. Monomers with fi can also be used.

Acrylic acid; Methacrylic acid; Itaconic acid; Maremono Shun;
Monoalkyl itaconate, such as monomethyl itaconate, monomethyl itaconate, itacon dispersion monofudernate; heptanoalkyl maleate, such as monomethyl maleate, monoethyl maleate, motuputil maleate, etc. Niditoraconic acid: Styrene sulfonic acid: Vinylbenzyl sulfonic acid: vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid, such as acryloyloxymethyl sulfonic acid, acryloyloxy7ethyl sulfonic acid,
Acryloyloxypropylsulfonic acid, etc.; Methacryloyloxyalkylsulfonic acid, such as Methac IJ
Qyloxymethylsulfonic acid, methacryloyloxydiethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; acrylamide alkylsulfonic acids, such as λ-acrylamido-co-methylethanesulfonic acid, -monoacrylamido-co-methylpropanesulfonic acid, co-acrylamido Dokometherbutanesulfonic acid, etc.: methacrylamide alcoholic acid, e.g.
Comethacrylamide--methylethanesulfonic acid,
-monomethacrylamido-methylpropanesulfonic acid, -monomethacrylamido-λ-methylbutanesulfonic acid, etc.; these acids may be salts of alkali metals (such as Na%) or ammonium ions.

Among the nine vinyl monomers listed above and other vinyl monomers used in the present invention, the hydrophilic seven vinyl monomers are
(Here, it refers to a material that becomes water-bathable when made into a homopolymer.) When using as a comonomer, as long as the copolymer does not become water-soluble, the proportion of hydrophilic monomer in the copolymer K, especially There is no limit, but usually 1, preferably 4
It is less than LO mulch, more preferably -0 mulch or less, more preferably 1 o-e mulch or less. 191 When the hydrophilic comonomer to be copolymerized with the monomer of the present invention has an acid group, the proportion of the comonomer having an acid group in the copolymer is usually , 20
It is less than 10%, preferably less than 10%, and most preferably does not contain any such comonomer.

The seven polymers of the present invention in the polymer are preferably methacrylate-based, acrylamide-based and methacrylamide-based.

(B) Polyester resin obtained by condensation of polyhydric alcohol and polybasic acid The polyhydric alcohol is HO-11□-〇H (R is a hydrocarbon chain having 4 to about 1λ carbon atoms, especially aliphatic Glycols or polyalkylene glycols having a hydrocarbon chain structure are effective, and as polybasic acids, HOO
Those having C-R2-COOH (where 2 represents a simple bond or a hydrocarbon chain having 1 to about 7.2 carbon atoms) are effective.・ Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol,
l Cope 0 Pyrene Glycol, l.

3-propylene glycol, trimethylolpronone,
/, 4! -butanediol, isobutylenediol, 1
．． ! - is nonanediol, neointyl glycol, l
1 hexanediol, 1.

7-hebutanediol, i, r-octanediol, l
l? -nonanediol, /, 10-decanediol, i
, ii-undecanediol, l.

l code decanediol, /, /J-) lysocandiol, /, tri-diol, glycerin, diglycerin,
Examples include triglycerin, l-methylglycerin, erythritol, mannitol, sorbitol, and the like.

Specific examples of polybasic acids include Scheric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azediic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and undecanedicarboxylic acid. Dodecanedicarboxylic acid, 7-malic acid, maleic acid, itaconic acid, citraconic acid, 7-talic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, methaconic acid, isohimelic acid, cyclopentadiene-maleic anhydride adduct, rosin- Examples include maleic anhydride and additives.

(C) Other examples include polyesters obtained by ring-opening polymerization as shown below.In the formula, mti represents an integer from 7 to 7. The -CH,- chain may be branched.

Suitable monomers that can be used in this polyester include β-propiolactone, ε-caprolactone, 1-
and dimethylpropiolactone.

The molecular weight and degree of polymerization of the polymer of the present invention have no substantial effect on the effects of the present invention as long as they exceed a certain level.
If the molecular weight is too high, it will take time to dissolve in a high boiling point V1 solvent or auxiliary solvent, and the solution viscosity will be high, making it difficult to emulsify and disperse, resulting in problems such as the formation of large particles and reduced color development. becomes more likely to occur. Therefore, the molecular weight of the polymer that can be used in the present invention is preferably 1 million or less and 2,000 or more, more preferably 400,000 or less and 5,000 or more, and still more preferably 150,000 or less and 10,000 or more.

The ratio of polymer to auxiliary solvent when preparing an emulsified dispersion containing the polymer of the present invention varies depending on the type of polymer used, and depends on the solubility in the auxiliary solvent, the degree of polymerization, etc., or the solubility of the coupler. Varies over a wide range 0 Generally, at least the coupler, high-boiling organic solvent, and polymer are dissolved in the auxiliary organic solvent, and the solution is easily dispersed in water or an aqueous hydrophilic colloid solution. The amount of auxiliary organic solvent necessary to provide a sufficiently low viscosity is used. The higher the polymerization degree of the polymer, the higher the viscosity of the solution, so it is difficult to uniformly determine the ratio of the polymer to the auxiliary organic solvent regardless of the polymer species, coexisting couplers, and high boiling point organic solvents. Usually 〇,
A range of 2 to 1:50 (weight ratio) is preferred.

The polymers or copolymers of the present invention may be used alone, or in combination of two or more, and even with polymers other than the present invention, as long as the effects of the present invention are not lost. Different polymers may be used in different layers in the photosensitive material.

Specific examples of the polymer used in the present invention are shown below, but the present invention is not limited thereto.

P-1) Poly(vinyl acetate) P-2) Poly(vinyl propionate) P-3) Poly(
Methyl methacrylate) P-4) Poly(ethyl methacrylate) P-5) Poly(ethyl acrylate) P-6) Poly(heptyl acrylate) P-7) Poly(
butyl acrylate) P-8) Poly(butyl methacrylate) P-9) Poly(
iso-butyl methacrylate) P-10) poly(is
o-propyl methacrylate-I) P-11>Poly(octyl acrylate) P-12) Poly(hexadecyl acrylate) P-13) Poly(hexyl acrylate) P-14) Poly(iso-butyl acrylate) P-15> Poly(iso-propyl acrylate) P-16) Poly(3-methoxybutyl acrylate) P-17) Poly(2-methoxycarbonylphenyl acrylate) P-18) Poly(3-methoxycarbonylphenyl acrylate) -1~) P-19) Poly(4-methoxycarbonylphenyl acrylate) P-20) Poly(2-methoxyethyl acrylate) P-21> Poly(4-methoxyphenylacrylate) P-22) Poly(3-methoxy) ethyl acrylate) P-23) Poly(methyl acrylate) P-24> Poly(3,5-dimethyladamantyl acrylate) P-25) Poly(3-dimethylaminophenyl acrylate) P-26> Poly(2-cyanmethylphenyl methacrylate) P-27>Poly(4-cyanophenyl methacrylate-1)
) P-28) Poly(decyl methacrylate) P-29) Poly(dodecyl methacrylate) P-30> Poly(diethylaminoethyl methacrylate) P-31) Poly(ethyl methacrylate) P-32) Poly(2-ethylsulfinylethyl methacrylate) Ray-1-) P-33) Poly(hexadecyl methacrylate) P-3
4> Poly(hexyl methacrylate) P-35) Poly(
2-Hydroxypropyl methacrylate) P-36) Poly(4-methoxycarbonylphenyl methacrylate) P-37) Poly(3,5-dimethyladamantyl methacrylate) P-38) Poly(dimethylaminoethyl methacrylate) P-39) Poly( 3,3-dimethylbutyl methacrylate) P-40) Poly(3,3-dimethyl-2-butyl methacrylate-1-) 13-41) Poly(3,5,5-1-limethylhexyl methacrylate) P- 42) Poly(octadecyl methacrylate) P-4
3) Poly(tetradecyl methacrylate) P-44 > Poly(pentyl acrylate) P-45) Poly(4-butoxycarbonylphenyl methacrylamide) P-46') Poly(pentyl methacrylate) P-47
) Poly(4-carboxyphenyl methacrylamide) P-48> Poly(4-oxycarbonylphenyl methacrylamide) P-49) Poly(4-methoxycarbonylphenyl methacrylamide) P-50) Poly(butyl butoxycarbonyl) methacrylate) P-51) Poly(butyl chloroacrylate) P-52
) Poly(butyl cyanoacrylate) P-53) Poly(
Cyclohexylchloroacrylate) P-54) Poly(ethylchloroacrylate) P-55
) Poly(ethyl ethoxycarbonyl methacrylate) P-56) Poly(N-sec-butylacrylamide) P-57) Poly(N-ter-butylacrylamide) P-58) Poly(ethyl methacrylate) P-59>Poly(cyclo hexyl methacrylate) P-60) poly(
Ethylfluoromethacrylate) P-61) Poly(hexylhexyloxycarbonyl methacrylate) P-62) Poly(ter-butyl methacrylate) P-
63) Poly(iso-butyl chloroacrylate) P-64) Poly(N-ter-butyl methacrylamide) P-65) Poly(iso-propyl chloroacrylate) P-66) Poly(methyl chloroacrylate) P-67
) Poly(methylfluoroacrylate) P-68) Poly(methylfluoromethacrylate) P-69) Poly(methylphenylacrylate) P-70) Poly(benzyl acrylate) P-71) Poly(4-biphenylacrylate) P-72 ) Poly(4-butylacrylate) P-73) Poly(sec-butyl acrylate) P-7
4) Poly(ter-butyl acrylate) P-75) Poly(2-ter-butylphenyl acrylate) P-76) Poly(4-ter-butylphenyl acrylate-1.) P-77) Poly[3-chloro -2,2-bis(chloromethyl)propyl acrylate] P-78>Poly(2-chlorophenylacrylate) P-79);
~) P-80) Poly(pentachlorophenylacryle-1~)
) P-81) Poly(4-cyanobenzyl acrylate) P-82) Poly(cyanoethyl acrylate) P-83
) Poly(4-cyanophenyl acrylate) P-84') Poly(4-cyano-3-butyl acrylate) P-85) Poly(cyclohexyl acrylate) P-8
6>Poly(2-ethoxycarbonylphenyl acrylate) P-87) Poly(3-ethoxycarbonylphenyl acrylate) P-88) Poly(4-ethoxycarbonylphenyl acrylate) P-89>Poly(2-ethoxyethyl) acrylate) P-90) Poly(3-ethyl)-xypropyl acrylate) P-91>Poly(IH,LH,5H-octafluoropentyl acrylate) P-92) Poly(propylchloroacryle-1-)P-
93>Poly(2-methylbutyl acrylate) P-94
) Poly(3-methylbutyl acrylate) P-95) Poly(l,3-dimethylbutyl acrylate) P-96) Poly(2-methylpentyl acrylate) P-97) Poly(2-naphthyl acrylate) P-98
) Poly(phenylacrylate) P-99) Poly(propyl acrylate) P-100> Poly(m-tolyl acrylate) P-101) Poly(0-tolyl acrylate) P-102) Poly(p-tolyl acrylate) P- 1
03) Poly(N-butylacrylamide) P-1,04
) Poly(N,N-dibutylacrylamide) P-105>Poly(N-iso-hexylacrylamide) P-106>Poly(N-iso-octylacrylamide) P-107>Poly(N-methyl-N-phenylacrylamide) ) P-108) Poly(adamantyl methacrylate) P-
109) Poly(benzyl methacrylate) P-110)
Poly(2-bromoethyl methacrylate) P-111) Poly(2N-ter-butylaminoethyl methacrylate) P-112) Poly(sec-butyl methacrylate) P-113>Poly(2-chloroethyl methacrylate) P-114) Poly(2-cyanoethyl methacrylate) P-115) 1,4-butanediol-adipic acid polyester P-116) Ethylene glycol-sebacic acid polyester P-117) Polycaprolactone P-118) Polyproviolacone P-119 ) Polydimethylpropion lactone P-12
0) Vinyl acetate-vinyl alcohol copolymer (95:5
) P-121) Butyl acrylate-acrylamide copolymer (95:5) P-122) Stearyl methacrylate-acrylic acid copolymer (90:10) P-123>Butyl methacrylate-N-vinyl-2-
Pyrrolidone copolymer (90: P-124) Methyl methacrylate-vinyl chloride copolymer (70: 30) P-125) Methyl methacrylate-styrene copolymer (90:10) P-126) Methyl methacrylate-ethyl acrylate copolymer Polymer (50: 50) P-127>Butyl methacrylate-methyl methacrylate-styrene copolymer (50: 30: 20> P-128) Vinyl acetate-acrylamide copolymer (4C
(85:15) P-129> Vinyl chloride-vinyl acetate copolymer (65:
35) P-130) Methyl methacrylate-acrylonitrile copolymer (65: 35) P-131) Diacetone acrylamide-methyl methacrylate copolymer (50:5゛0) P-132) Methyl vinyl ketone-1so-butyl Methacrylate copolymer (55: P-133) Ethyl methacrylate-butyl acrylate (70: 30) P-134>Diacetone acrylamide-butyl acrylate copolymer <60:40) P-135) Methyl methacrylate-styrene methyl methacrylate- Diacetone acrylamide copolymer (40:40:20) P-136) Butyl acrylate-styrene methacrylate-diacetone acrylamide copolymer (70:20:10) P-137)
Stearyl methacrylate-methyl methacrylate-acrylic acid copolymer (50:40:10) P-138) Methyl methacrylate-styrene-vinyl sulfonamide copolymer (7 0:20:10) P-139>Methyl methacrylate-phenyl vinyl Ketone copolymer <70: 30) P-140) Butyl acrylate-methyl methacrylate-butyl methacrylate copolymer (35: 35: 30) P-141) Butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer Combined (38:38:2 P-142) Methyl methacrylate-butyl methacrylate-1so-butyl methacrylate-acrylic acid copolymer (37: 29: 25: 9) P-143) Butyl methacrylate-acrylic acid copolymer ( 95:5) P-144> Methyl methacrylate-acrylic acid copolymer (95:5) P-145) Benzyl methacrylate-acrylic acid copolymer (90:10) P-146) Butyl methacrylate-methyl methacrylate-benzyl methacrylate - Acrylic acid copolymer (35:35:25:5) P-147) Butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (35:30:35) P-148) Cyclohexyl methacrylate-methyl methacrylate-
Propyl methacrylate copolymer (37: 29: P-149) Methyl methacrylate-butyl methacrylate copolymer (
65: 35) P-150) Vinyl acetate-vinyl probionate copolymer (75: 25) P-151) Butyl methacrylate-3-acryloxybutane-1-sodium sulfonate copolymer (97: 3) P- 152>Butyl methacrylate-methyl methacrylate-acrylamide copolymer (35: 35: 30) P-153) Butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37: 36: 27> P-154) Butyl methacrylate-styrene copolymer Polymer (90:10) P-155) Methyl methacrylate-N-vinyl-2-
Pyrrolidone copolymer (90: 1)-156>Butyl methacrylate-vinyl chloride copolymer (90:10) P-157) Butyl methacrylate-styrene copolymer (70: 30) P-158) Diacerone acrylamide - Methyl methacrylate copolymer (62:3 P-159) N-ter-butylacrylamide-methyl methacrylate copolymer (40:60) P-160) ter-butyl methacrylate-1-methyl methacrylate copolymer ( 70:30) P-161) N-ter-butylacrylamide-
Methylphenyl methacrylate copolymer (60:40) P-162) Methyl methacrylate-acrylonitrile copolymer (70:30) P-163) Methyl methacrylate-methyl vinyl ketone copolymer (38:72) P-164) Methyl methacrylate-styrene copolymerization f
Water (75: 25) P-165) Methyl methacrylate-1-1-hexyl methacrylate-1 copolymer (70: 30) P-166>N-
Methyl-N-benzylacrylamide-butyl acrylate-dibutyl fumarate copolymer (55:35:10) P-167) poly(N-(1,1-dimethyl-3=oxobutyl>acrylamide) P-168) poly( N-octylmethacrylamide) P-169) N,N-diethylacrylamide-butyl acrylate-I ~ copolymer (40:60) P-170) N,N-diethylacrylamide-2-butyl acrylate-xyethyl acrylate copolymer Combined (65: 35) P-171) N-ter-butylacrylamide-butylacrylate copolymer (6 Q:40) P-172) N-1er-octylacrylamide-2
-Ethylhexyl acrylate copolymer (65:35) P-173) N,N-dibutylacrylamide-dibutyl maleate copolymer (75:25) P-174)N-(1,1-dimethyl-3- (oxobutyl)acrylamide-butyl acrylate copolymer (55:45) P-175>N-(1,1-dimethyl-3-oxobutyl)acrylamide-butyl acrylate copolymer (70:30)P-176)N
-ter-butylacrylamide-butylacrylate copolymer (4 5: 55) P-177) N-octyl-N-ethylacrylamide-ethyl acrylate copolymer (45:55> P-178) N-butylmethacrylamide- 2-ethylhexyl acrylate copolymer (90:10) P-179) N,N~dibutylmethacrylamide-propyl acrylate-1~copolymer (80:20) P-180)N-(2-phenyl Ethyl) acrylamide-butyl acrylate copolymer (25: 75) P-181) N-acryloylmorpholine-2-ethoxyethyl acrylate (40:60) P-182) N-methyl-N-acryloylpiperazine-butyl acrylate 1 to copolymer (15:85) P-183) N-acryloylpiperidine-2-butoxyethyl acrylate copolymer (40:60) P-184) N-(1.1-dimethyl-3-hydroxybutyl) Acrylamide-2-ethylhexyl methacrylate copolymer (75: 25) P-185) N-acryloylpiperidine-butyl acrylate copolymer (50: 5 P-186) N-<p-hydroxyphenyl) acrylamide-butyl acrylate Copolymer (25: 75) P-187) N-(3-(dimethylamino)propylcoacrylamide-butyl acrylate copolymer (35: 65) P-188) N-methyl-No-methacryloyl,
Piperazine-2-ethoxyethyl acrylate copolymer (40:60) P-189) 2,6-dimethyl-4-methacryloylmorpholine-butylacrylate copolymer (55:45) P-190) N-ter-butylacrylamide- Butyl acrylate-2-ethoxyethyl acrylate copolymer (55:25:20) P-191) N-(1,1-dimethyl-3-oxobutyl)acrylamide-butyl acrylate-N,N-diethylacrylamide copolymer ( 30: 50: 20) P-192) N-methyl-No-methacryloylpiperazine-2-ethoxybutyl acrylate-ethyl acrylate copolymer (30: 40: 30) P-193) 1.6-hexanethiol-ascorbin Acid - Sebacic acid polyester P-194) Diethylene glycol - Adipic acid polyester P-195)) Limethylolpropane - Adipic acid - Phthalic acid polyester P-196) Diethylene glycol - Trimethylolpropane - Adipic acid polyester P-197) Ethylene glycol - Adipic acid polyester P-198) Ethylene glycol-1,4-butanediol-adipic acid polyester P-199) 1,4-bis-(β-hydroxyethoxy)benzene-sebacic acid polyester P-200) Ethylene glycol-azelaic acid Polyester Next, the diffusion-resistant oil-soluble graphite used in the present invention will be described in detail.

What is the diffusion-resistant oil-soluble coupler mentioned here?

This refers to a coupler that is soluble in a high-boiling organic solvent, which will be described later, and has been made diffusion resistant so that it is difficult to diffuse in a photographic light-sensitive material. For example, the following methods can be used to make the coupler resistant to diffusion.

First, an aliphatic group having a molecular weight above a certain level,
This is a method in which one or more so-called diffusion-resistant groups containing an aromatic group or a heterocyclic group in the partial structure are introduced into the molecule. The total number of carbon atoms constituting the diffusion-resistant group is usually preferably 6 or more,
More preferably, the number is 12 or more. Two coupler molecules may be linked via some kind of diffusion-resistant group, etc., and the molecular weight of these couplers is 250 per coupler molecule.
-2000 is preferable, more preferably 300-150
It is 0. The second method is to form a polymer coupler by using the coupler as a multimer, and increase the molecular weight to make the coupler resistant to diffusion.

The cyan coupler used in the present invention will be further explained.

'In the general formulas (1') and (■), Yl and the detachable group represented by Yl include, for example, a halogen atom (
(fluorine atom, chlorine atom, bromine atom), sulfo group, alkoxy group, acyloxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, and the like.

R1, R4 and R5 are each preferably an aliphatic group having 1 to 36 carbon atoms, preferably 6 to 36 carbon atoms.
aromatic groups (e.g., phenyl group, naphthyl group, etc.), heterocyclic groups (e.g., 3-pyridyl group, 2-furyl group, etc.), or aromatic or chlorocyclic amino groups (e.g., anilino group, naphthylamino group, - one penzothiazolyl amino group,
- monopyridylamino group, etc.), and these groups are
Further, an alkyl group, an aryl group, a v1 uncyclic group, an alkoxy group (eg, methoxy group, comethoxyethoxy group, etc.), an aryl group (eg, comethoxyethoxy group, etc.), and an aryl group (eg, comethoxyethoxy group, etc.).

a-di-tert-amylphenoxy M, s-chlorophenoxy group, cucyanophenoxy Mfx, etc.), alkenyloxy group (e.g., -1propenyloxy group, etc.), acyl group (e.g., acedel group, benzoyl group, etc.)
, ester groups (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, penzoyloyl group, butoxysulfonyl group, toluenesulfonyloxy group), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methane group) sulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g., dipropylsulfamoylamino group, etc.), imide group (e.g., succi/imide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethyl ureido group, etc.), aliphatic or aromatic sulfonyl group (e.g., t, /l tansulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxy7 The substituent may be substituted with a group selected from a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom, and the like.

As used herein, the term "aliphatic group" refers to a linear, branched, or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl, and alyanyl groups. Typical examples include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, and icosenyl Lis.

Examples include -propyl group, tert-butyl group, tert-octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, cohexadecenyl group, and propargyl group.

- In the pattern hole (1), R2 is preferably carbon number/~2Q
represents an aliphatic group and may be substituted with RIK-permitted substituents.

In general formula (1) and general formula (II) Ic, R3 and R6 each represent a hydrogen atom or a halogen atom (for example,
fluorine atom, chlorine atom, bromine atom, etc.), preferably an aliphatic group having a carbon number of /~-〇, preferably an aliphatic oxy group having a carbon number of /~-〇, or preferably an acylamino group having a carbon number of /~-〇 (e.g. acetamide group, penzamide group,
(tetradecanamide group, etc.), and these aliphatic groups, aliphatic oxy groups, and acylamino groups may be substituted with permissible substituents for R1.

In the general formula [(], R2 and R3 jointly! to 7
It may form a member item.

- R5 and R6 collaborate in Monana CII)! or may form a Z-membered ring.

- Dimerization by any of R1, R2, R3 or Yl in Monnai (1), or - any seven groups of R4, R5R6 or Yl in Monnai [11) independently or jointly. The above multimer turnip 2- may be formed.

In the case of dimers, these groups can be used as simple bonds or as divalent linking groups (e.g., divalent groups such as alkylene groups, arylene groups, ether groups, ester groups, amide groups, and divalent groups that combine these groups). When forming oligomers or polymers (e.g., divalent groups), these groups may be in the polymer backbone or may be attached to the polymer backbone through divalent groups as described for dimers. preferable. When forming a polymer, even if it is a homopolymer of the coupler rust conductor, other non-color-forming ethylene-like monomers (for example, acrylic acid, methacrylic acid, methyl acrylate, n-butylacrylamide, β-hydroxy methacrylate, (vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride, N-vinylpyrrolidone, etc.).

- Monna (preferred R1 and general formula (n) in IN)
Preferred R5 is substituted or unsubstituted,
It is an alkyl group or an aryl group, and as a substituent for the alkyl group, a phenoxy group or a halogen atom which may be substituted is particularly preferable (as a substituent for the phenoxy group, an alkyl group, an alkoxy group, a halogen atom, a sulfonamide group , sulfamide group is more preferred), and the aryl group is particularly preferably a phenyl group substituted with at least one halogen atom, alkyl group, sulfamide group, or acylamino group.

In general formula (n), R4 is preferably a substituted alkyl group or a substituted or unsubstituted aryl group, and as a substituent for the alkyl group, a norogen atom is particularly preferable, and the aryl group is a phenyl group, a norogen atom, or a sulfone Particularly preferred is a phenyl group substituted with at least 7 amide groups.

- R2, which is most preferred in (1), is an alkyl group having 1 to 20 carbon atoms even if it is substituted.

Preferred substituents for R2 include an alkyl or arylamino group, an acylamino group, an alkyl or arylthio group, an imido group, a ureido group, and an alkyl or arylsulfonyl group.

- In maximum [1], R3 is preferably a hydrogen atom, a chlorine atom (especially a fluorine atom or a chlorine atom), or an acylamino group, with a chlorine atom being particularly preferred.

In the general formula (II), 几6 is preferably a hydrogen atom, an alkyl group or an alkenyl group having a carbon number of 0 to 0, and a hydrogen atom is particularly preferable.

In the general formula […], R5 and R6! It is preferable that a nitrogen-containing complex tree term of 6- to 6-membered terms is formed.

In general formula (1), lζ2 is more preferably an alkyl group having 4 to 4 carbon atoms.

The magenta coupler that can be used in the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. ! - As for the pyrazolone couplers, couplers in which the 3-position is substituted with an arylamino group or an acylamino group are preferred from the viewpoint of the hue and coloring density of the coloring dye, and representative examples thereof include U.S. Pat. 2nd゜j
4tJ, No. 702, No. 2, 40σ121r, No. 01.173, No. 3. θ6, GojJ, $3. /J, 2. ♂No. 26 and 3゜936, θ/
! It is written in the number etc. Two equivalents! - U.S. Pat. No. 3, 3/θ, 6/
No. 9 or the nitrogen atom leaving group described in U.S. Pat.
The arylthio group described in Jj/, No. 197 is preferred. Also, European Patent No. 73. jJ has the ballast group described in the issue! - Pyrazolone couplers provide high color density.

As pyrazoloazole couplers, US Pat.
jj? ,? Pyrazolobenzimidazoles as described in US Pat. No. 7F, preferably U.S. Pat.
Liazoles, Research Disclosure 'l'-29
1220 (June 797g) Pyrazolotetrazoles described in VC and Research Disclosure Cog λ3
Examples include pyrazolopyrazoles described in 0 (/ri/da, June 2013). European Patent No. 119,741 G: Imidazo [1
, 2-b) pyrazoles are preferred, as described in European Patent No. 119
, pyrazolo (1,5-b) (1,2,
4) Triazoles are particularly preferred.

These couplers are represented by the following general formula.

In this maximum, R1 represents a hydrogen atom or a substituent, including an alkyl group (e.g. methyl group, ethyl group, butyl group, etc.), a branched alkyl group (e.g. isopropyl group, isobutyl group, tertiary butyl group, etc.), a substituted Alkyl group (
(branched), alkoxy groups (e.g., methoxy, ethoxy, butoxy, etc.), substituted alkoxy groups (e.g., ethoxyethoxy, phenoxyethoxy), aryloxy groups (e.g., phenoxy, etc.), ureido groups, etc. are particularly preferred. Branched alkyl groups and alkoxy groups are preferred, X
represents a hydrogen atom or a group that can be degraded by a coupling reaction with an oxidized bed of an aromatic primary amine color developing agent. Examples of such groups include halogen atoms (for example, chlorine atoms, bromine atoms, etc.), arylthio groups (rFA, For example, 2-butoxy-5-tert-octylphenylthio group, 2-propoxy-5-tert-hexylphenylthio group, etc.), nitrogen-containing heterocyclic group (e.g., imidazole group, 4-chloroimidazole group, etc.), aryloxy groups (e.g. p-methylphenoxy group, 2.4-dimethylphenoxy group, 2.
4-dimethyl tertiary phenoxy group, etc.). Among these, halogen atoms and arylthio groups are particularly preferred; Za, Zb and Zc are methine,
Represents substituted methine or =N-1-NH-, Za-
One of the Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. When Za-Zb is a carbon-carbon double bond, it also includes the case where it is part of an aromatic ring.
Furthermore, it also includes the case where a dimer or more multimer is formed with R1t or include. When Za-Zb or Zc represents a substituted methine, the substituent is preferably a substituted alkyl group, particularly a branched substituted alkyl group (for example, a substituted isopropyl group, a substituted tertiary butyl group, etc.).

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2.40
No. 7,210, No. 2,875.057 and No. 3
．． 265.506 etc. The present invention includes:
The use of two-equivalent yellow couplers is preferred, and U.S. Pat.
Oxygen atom separation type yellow couplers described in Japanese Patent Publication No. 58-10739, U.S. Patent No. 4.40, etc.
No. 1,752, No. 4,326゜024, RD180
53 (April 1979), British Patent No. 1,425.0
No. 20, West German Application No. 2,219,917, No. 2
．． Typical examples thereof include the nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 261.361, 2.329.587, and 2.433.812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

In the present invention, the ratio of coupler to polymer is preferably 1:0.05 to 1:20 by weight, more preferably 1:0.1 to 1:10.

The coupler used in the present invention is usually contained in the silver halide emulsion layer in an amount of 0.005 to 4 mol, preferably 0.05 to 2 mol, per mol of silver halide.

Furthermore, the coating amount on the support is 2 x 10-5 mol/pol 1 x 1
0-2 mol/n (preferably, 4 x 10-5 mol/rrr to 5 x 10-3-11 mol/rrr).

Preferred specific examples of the cyan coupler according to the present invention are described below, but the invention is not limited thereto.

(C-/n(C-ko) (C-s) Cε (C-a) (e (C-t) (C-, <) ! (C-7) (C-, r) (C- ta) (C-10) α (C7//) α (C-/, 2) α (C-/3) (C-74t) No. 1 (c-ij) (C-/a) (C-/ J'') (C-/y) (C-,2(7) (C-2/) (C-2g) (C-2t) (C-,zt) (C-=7) (C-co ♂) (C-so) (C-j/) (C-3J) (C-3da) (C-jj) (C-J'4nCC-37) (C-da3) LJfl (C- 4t4t) (C-4tJ) 5-pyrazolone couplers and virazoloasole couplers are preferably used as marvinta couplers.

Below, pour one row of magenta coupler ingredients preferably used in the present invention.

(M-/) α CM-2) α (M-J) し8M17(t) (M-9) (M-r) (M-O) α (M-)) (M-ta) (M- io) (M-//) (M-/, 21 (M-/3) CH3 Take CH2NHs02CH3 (M-/4t) ShisHolZ) CM-yrn (M-/ni) Shiskl17(t) CM-/ y) (M-7z) Shis H17 (Similarly, as a yellow coupler that can be used by emulsifying and dispersing with a high boiling point organic solvent and a polymer,
α-pivaloylacetanilide couplers are preferably used from the viewpoint of the balance of color image fastness, and specific examples thereof include the following compounds.

(, Y-/) し1t3 (Y-co) (Y-J) (Y-g) (Y-j) (Y-, <) (Y-7) (Y-, r) In the present invention, With these couplers, for example with pyrazoloazole couplers, compounds such as those described below can be used.

That is, a compound (A) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, the use of a compound (B) that chemically bonds with the oxidized bed of a group amine color-forming agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly, for example, during storage after treatment. This is preferable in order to prevent the occurrence of staining and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized bed remaining in the film and the coupler.

A preferable compound (A) has a second-order reaction rate constant 1 (2 (in trioctyl phosphate at 80°C) with p-anisidine of 1.0 Q/mol·sec~l
It is a compound that reacts in the range of X 10-51/mol-sec.

When k2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention.

A more preferable compound (A) can be represented by the following formula (A4) or (All).

General formula (AI) R1-(A)n-X General formula (A■) R2-C=Y In the formula, f'(1 and R2 are an aliphatic group, an aromatic group,
or represents a heterocyclic group, n represents 1 or 0.

B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents the addition of an aromatic amine developing agent to the compound of general formula (A■). Represents a promoting group, where RI and X, Y and R2 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

Each group of the compounds represented by the general formulas (AI) and (AI) will be explained in more detail.

The aliphatic group in R1, R2 and B represents a linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group, which may be further substituted with a substituent. The aromatic group is either a carbocyclic aromatic group (e.g., phenyl group, naphthyl group, etc.) or a heterocyclic aromatic group (e.g., furyl group, thienyl group, pyrazolyl group, pyridyl group, indolyl group, etc.). Both monocyclic and condensed ring systems (e.g. benzofuryl group,
phenane 1-lysinyl group, etc.), and furthermore, these aromatic rings may have a substituent.

The heterocycle in R1, R2 and B is preferably a group having a 3- to 10-membered ring structure composed of carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms or hydrogen atoms, and the heterocycle itself is a saturated ring. may be present, and may be further substituted with a substituent (e.g., cumanyl group, pyrrolidyl group,
pyrrolinyl group, morpholinyl group, etc.).

X represents a group that reacts with an aromatic amine developing agent and leaves the group, and is a group that is bonded to A via an oxygen atom, sulfur atom, or nitrogen atom (e.g., 3-pyrazolyloxy group, 31-1-
(1.2.4-oxadiazolin-5-oxy group, aryloxy group, alkoxy group, alkylthio group, arylthio group, substituted N-oxy group, etc.) or a halogen atom.

λ represents a group that reacts with an aromatic amine developing agent to form a chemical bond, and in the case of an atom containing an atom with a low electron density, n represents 0, where L is an R″′ single bond. , alkylene group, -0-1-S-1-N-1 sulfonyl group, sulfinyl group, oxycarbonyl group, posbonyl group, thiocarbonyl group, aminocarbonyl group, silyloxy group, etc.).

Y has the same meaning as Y in general formula (All), and Y.

does not have the same meaning as Y.

R゛, R'' may be the same or different, and each -
Represents L゛-Ro.

Ro represents the same meaning as R1, R" represents a hydrogen atom, an aliphatic group (e.g. methyl group, isobutyl group, 1-butyl group, vinyl group, benzyl group, octadecyl group, cyclohexyl group, etc.), aromatic group (e.g. phenyl group, pyridyl group, naphthyl group, etc.), hetero IJ2 (e.g. piperidinyl group,
Pyranyl group (furanyl group, chromanyl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), and sulfonyl group (eg, methanesulfonyl group, benzenesulfonyl group, etc.).

L', L", and R49 are preferably 10-5-S-1 and a group.

Y in general formula (A■) is an oxygen atom, a sulfur atom, =N-R4
and =C-R6 are preferred.

Here, R4, R5 and R6 are hydrogen atoms, aliphatic groups (e.g. methyl group, isopropyl group, t-butyl group, vinyl group, benzyl group, octadecyl group, cyclohexyl group, etc.), aromatic groups (e.g. phenyl group, pyridyl group, etc.). group, naphthyl group, etc.), heterocyclic group (e.g., piperidyl group, pyranyl group, furanyl group, chromanyl group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, benzenesulfonyl group, etc.) ), and R5 and R6 may be bonded to each other to form a cyclic structure.

A compound (B
) is preferable as the nucleophilic ncI-13I value of Pe-a l-S On (R, G, Pe-arson+e
t al+, J, A+n, Chern+Soc,, 9
0.319 (1968)) is a compound having a nucleophilic group derived from five or more nucleophilic functional groups.

A more preferable compound CB) is represented by the following general formula (Bo).

- Monka (B''') R7-Z-M In the formula, R7 does not represent an aliphatic group, aromatic group or heterocyclic group, Z represents a nucleophilic group, and 0M represents a hydrogen atom or a metal cation. , represents an ammonium cation or a protecting group.

Each group of the compound represented by the general formula (Bo) will be explained in more detail.

The aliphatic group represented by R7 represents a linear or cyclic alkyl group, alkenyl group, or alkynyl group, and may be further substituted with a substituent.

The aromatic group represented by R7 refers to a carbocyclic aromatic group (e.g., phenyl group, naphthyl group, etc.) and a heterocyclic aromatic group (e.g., furyl group, thienyl group, pyrazolyl group, pyridyl group, indolyl group, etc.) It may be either a monocyclic system or a condensed ring system (for example, a benzofuryl group, a phenan I/lysinyl group, etc.), and these aromatic rings may have a substituent.

The heterocyclic group referred to in R7 is a 3-membered ring composed of carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms or hydrogen atoms.
A group having a 0-membered cyclic structure is preferable, and the heterocycle itself may be a saturated ring or an unsaturated ring, and may be further substituted with a substituent (for example, a coumanyl group, a pyrrolidyl group, a pyrrolinyl group, etc.). , morpholinyl group, etc.).

Z represents a nucleophilic group, for example, a nucleophilic group in which the atom that directly chemically bonds with the oxidized bed of an aromatic amine developing agent is an oxygen atom, a sulfur atom, or a nitrogen atom (for example, an amine compound,
Azide compound, hydrazine compound, mercap 1-1 compound, sulfide compound, sulfinic acid compound, cyano f
H compounds, thiocyano compounds, thiosulfate compounds, seleno compounds, halide compounds, carboxy compounds, hydroxamic acid compounds, active methylene compounds, phenol compounds,
Nitrogen heterocyclic compounds, etc.) are known.

M represents a hydrogen atom, a metal cation, an ammonium cation or a protective group.

The compound represented by the -a formula (Bo) undergoes a nucleophilic reaction (typically a coupling reaction) with the oxidized bed of an aromatic amine developing agent.

Among the compounds represented by the -R formula (Bo), the most preferred are compounds represented by the following general formula (B'').

General formula (B'') 302M' In the formula, M' is an inorganic (e.g. Li, Na, K, Ca, Mg
etc.) or an atom/atom or atomic group forming an organic salt (e.g. triethylamine, methylamine, ammonia, etc.) and -NHN=C, \, where R15 and R16 may be the same or different, and each R15 and R represent a hydrogen atom or an aliphatic group, aromatic group or heterocyclic group having the same meaning as R1
16 may combine with each other to form a 5- to 7-membered ring, R
17, R18, R20 and R21 may be the same or different and each represents a hydrogen atom or an aliphatic group, aromatic group or heterocyclic group having the same meaning as R7, R17, R1
8, R20 and R21 further represent an acyl group, an alkoxycarbonyl group, a sulfonyl group, a ureido group and a urethane group.

(EI L, at least one of rt17 and R18, and at least one of 1120 and R21 are hydrogen atoms. R19 and R22 are hydrogen atoms or R
7 represents an aliphatic group, an aromatic group or a heterocyclic group, and R22 is an alkylamino group, an arylamino group,
Represents an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, etc., where at least two of R17, R18, and R19 are bonded to each other to form a 5- to 7-membered ring. Alternatively, at least two groups of R20 and r(21-R22 may be bonded to each other to form a 5-7R ring.

RIO, R11-R12, R13 and R14 may be the same or different, and each represents a hydrogen atom, an aliphatic group (e.g. methyl group, isopropyl group, t-butyl group, vinyl group, benzyl group, octadecyl group, cyclohexyl group, etc.)
, aromatic group (e.g. phenyl group, pyridyl group, naphthyl group, etc.), heterocyclic group (e.g. piperidyl group, pyranyl group, furanyl group, chromanyl group, etc.), halogen atom (e.g. chlorine atom, bromine atom, etc.), -5r (8, -0R8,
-N-r (8, acyl group (e.g. acetyl group, benzyl group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, butoxycarbonyl group, cyclohexylcarbonyl group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, benzenesulfonyl group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group,
ureido group, urethane group, carbamoyl group, sulfo group,
carboxyl group, nitro group, cyano group, alkoxy group (e.g. methoxyxalyl group, isobutoxyxalyl group, octyloxyxalyl group, penzoyloxyxalyl group, etc.), allylxalyl group (e.g. phenoxyxalyl group, Nano 1-xyxalyl group, etc.), sulfonyloxy group (e.g. methanesulfonyloxy group, benzenesulfonyloxy group, etc.), -P(R8)3, P(R8)2
, -P(R8)2, -P(OR8)3 and a formyl group, where R8 and R9 represent a hydrogen atom, an aliphatic group, an alkoxy group or an aromatic group.
Compounds having a sum of Hammet's σ values of 0.5 or more with respect to 2M' are particularly effective in the present invention.

Representative examples of compounds represented by the general formulas (A1), (A■), and (B゛) are listed below.

(A-1) 2H5 2H5 (A-4) c z I-15 03Na (A-5) 2H5 02Na (A-6) 11cA Z-
11 (A-19) (A-20) (A-21) (A-22) (A-23) (, l (,1 0.

1.

He = He = Ku
Kuku
Kud Engineering Q 0 1 (B-3) (B-4) (B-5) (B-6) 2H5 ■ 2H5 (B-7)! :0:0.

o ′ Q 1c/) a:1 zuν
Z zo o.

oo　　　　　　　o　　　　

1 of 1
co mco
Bow-J z v
7:.

(B-13) S02C18837 (B-14-H 12H25 (B-15) (B-16) Next, the high boiling point organic solvent used in the present invention will be described in detail.

The high boiling point organic solvent of the present invention has a boiling point of 140'C or higher, and can also be used with water having a melting point of 100°C or lower and a boiling point of 140'C or higher, other than -=a formula (ul) to -general formula (■). Any immiscible compound can be preferably used as a solvent for couplers and polymers.The melting point of the high-boiling organic solvent is preferably 80°C or lower.

The boiling point of the high boiling point organic solvent is preferably 160"C or higher, more preferably 170"C or higher.

When the melting point of the high-boiling organic solvent exceeds about 100° C., crystallization of the coupler tends to occur, and furthermore, the effect of improving color development tends to be poor.

In addition, if the boiling point of the high boiling point organic solvent is below approximately 140°C, it is likely to evaporate when the photographic emulsion is coated and dried, so it may form oil droplets in the photographic emulsion layer together with the coupler and the polymer of the present invention. They are difficult to coexist, and as a result, it is difficult to obtain the effects of the present invention.

Also, if the high boiling point organic solvent used is miscible with water,
When a photographic emulsion layer is coated, or when a photosensitive material obtained by coating and drying is photographically processed, the coupler may migrate to the photographic layer or leak into the processing solution, causing color mixing and fogging. and cause a decrease in maximum color density.

In the present invention, the preferred amount of the high boiling point organic solvent used is:
Although varying over a wide range depending on the type and amount of coupler and polymer, the high boiling organic solvent/coupler ratio is preferably:
Weight ratio of 0.05 to 20, more preferably 0.1 to 1
0, and the high boiling point organic solvent/polymer ratio is preferably 0.
．． 02 to 100, more preferably 0.05 to 5
It is 0.

Further, the high boiling point organic solvent can be used alone or in combination.

Among the compounds represented by general formulas (Ill) to (■),
The general formulas (Ill, ), (IV) and (■) are preferred.

-A substituted or unsubstituted alkyl group, cycloalkyl group represented by W1 to W6 in formulas (III) to (■),
As specific examples of the alkenyl group, aryl group and heterocyclic group, the groups exemplified with respect to general formulas (1) and (■) can be applied. Furthermore, an epoxy group may be bonded to the alkyl group.

Specific examples of high-boiling coupler solvents used in the present invention are shown below, but the invention is not limited thereto.

(S-/) 0=P+OC4Hg-n)a (S-, 2) 0=P40CH2CH2CHCH3) 3 drinks H3 (S-, r) 0=P+0C6H13-dan)3 (S-y) (S-t) (S-, <) o=p4ocsa17-dan)3 (S-7) (S-, r) (S-?) (S-10) 0=P+OCgH1g-dan)3 (S-/, 2) 0=P+0C10H21-dan)3 (S-/j) (S-/K) (S-/1) (S-/bu) (S-/7) (S-/1) (S-/ri) (S-10) (S-co/) (S-, 2, 2) 2H5 0=P(-OCH2CI(C4H9)2(S-, z3) (S-, 2g) (S-, zt) (S-2≦) (S-, 27) (S-, 2/) 2H5 C2H.

(S-30) C21(.

2H5 (S-37) (S-3,z) (S-33) (S-3g) (S-3t) (S-,za) (S-37) (S-3cr) (S-39) H3 (S-gu0) (S-4t/) (S-u,z) (S-yi) (S-guy) (S-9tr) (S-pa). 2□, 5 2H5 (S-g2) (S-4tt) (S-geta) C1(C00CI(2(CF2CF2)2HCHCOO
CH2(CF2CF2)2H(S-to) (S-t/) (S-tco) (S-t3) (S-rz) Cl2H250H(S-
z t ) C16H330H (S-!ri)
'Cl8H370)1(S-j/)
Cl0H210(CH2)50(CH2)20H(S
-! ri) (S-to) (S-t / ) CHa (CH2)17
(J(S-t, 2) CH3(CH2)
15Br (S-+3) (S-6g) CIIzCII2COOC112CIIC4J (gr C2H5 (S-gr) C2115 C00C112CIIC411,.

" (chi2).

C00CI 12CI IC411g [2H5 (S-6g) C112COOC112CIIC4119 (C112)
6 C■l2COOCII□acjl.

2JI5 An emulsified dispersion of lipophilic fine particles containing the coupler of the present invention, a high-boiling organic solvent, and a polymer is prepared as follows.

After codissolving the polymer of the present invention, which is a so-called non-crosslinked linear polymer synthesized by solution polymerization, emulsion polymerization, suspension polymerization, etc., a high boiling point organic solvent, and a coupler in an auxiliary organic solvent, This solution is dispersed into fine particles in water, preferably in a hydrophilic colloid solution, more preferably in an aqueous gelatin solution, using a dispersant by ultrasonic waves, a colloid mill, or other mechanical dispersion methods.

Alternatively, a dispersion aid such as a surfactant, the polymer 1 of the present invention,
Adding water or an aqueous solution of a hydrophilic colloid such as gelatin to a high boiling point organic solvent and an auxiliary organic solvent containing a coupler,
The auxiliary organic solvent may be removed from the prepared dispersion by a method such as distillation, noodle washing, or ultrafiltration. is an organic solvent useful during emulsification and dispersion, and is substantially finally removed from the photosensitive material by the drying process during coating or the method described above, and is a low boiling point organic solvent that can be removed by evaporation. , or a solvent that can be removed by washing with water, etc. Examples of auxiliary organic solvents include acetate-1-1-, such as ethyl acetate and butyl acetate, butyl carpitol acet-1-110, ethyl pionate, secondary butyl alcohol, methyl ethyl-1- Examples include methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and cyclohexanone.

Furthermore, an organic solvent completely miscible with water, such as methyl alcohol, ethyl alcohol, acetone, or tetrahydrofuran, can also be used in part.

Moreover, these organic solvents can be used in combination of two or more types.

The average particle size of the hydrophilic fine particles thus obtained is 0.
0.03 μ or more and 2 μ or less, more preferably 0.0
It is 5μ or more and 0.4μ or less. The particle size of the oil-based fine particles can be measured, for example, using a device such as J-Nosizer manufactured by Coulter.

Various substances useful for photography can be contained in the t31 oily fine particles of the auxiliary organic solvent.

Examples of materials useful for photography include colored couplers,
Colorless couplers, imitation agents, developer precursors, development inhibitor precursors, ultraviolet absorbers, development accelerators, hydroquinones, quinones, dyes, dye release agents, antioxidants, optical brighteners, antifading agents In the present invention, it is often preferable to use these together for υF.

In addition, as substances useful for photography contained in the lipophilic fine particles of the present invention comprising a coupler, a high-boiling organic solvent, and a polymer, the compounds of the following general formulas (A) to (C) are the colorants of the present invention. It is particularly useful for enhancing the effects of improving image fastness and color development.

'・Q' A represents a divalent electron-withdrawing group, R1 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group , represents a substituted or unsubstituted alkylamino group, a substituted or unsubstituted anilino group, or a substituted or unsubstituted heterocyclic group. l is/or an integer. 1ζ2 represents a substituted or unsubstituted alkyl group, [1% or unsubstituted alkoxy group, hydroxyl group, or halogen; m is an integer from θ to G; Q
represents a ``P747 term or a ``hete'' term condensed to a pheno-# term.

It is a silamino group.

Specific examples of compounds represented by nine general formulas (A) to (C) are listed below, but the invention is not limited to these.

X-7) X-, 2) X-3) X- to X-) X-2) X-, r) X-? ) X-70) X-//) X / -2) X-/j) X-/Da) X-/Ma) X-7g) X-/7) X-/J') X-7? ) The silver halide emulsion used in the present invention is mainly composed of (1
A silver chlorobromide emulsion containing substantially no silver iodide, consisting of silver chloride, silver bromide, or a mixed crystal thereof surrounded by 00) planes. "Substantially free of silver iodide" means that the content of silver iodide is 3 mol% or less, preferably 1 mol% or less, based on the total amount of silver halide. More preferably, it is 0.5 mol % or less, and most preferably, it does not contain any silver iodide. Containing silver iodide increases the amount of light absorption in terms of photosensitivity, strengthens the adsorption of spectral sensitizing dyes,
Alternatively, there are many useful features such as weakening the desensitization caused by spectral enhancing dyes, but when performing rapid development in a short period of time with the system using the technology of the present invention, the slow development speed is important for the entire silver halide grain. Although containing silver iodide in an amount of 0.4 mol% or less may be advantageous in terms of adsorption of spectral sensitizing dyes, etc., in the present invention It is preferable to use a silver halide emulsion that basically does not contain silver iodide.

The silver chlorobromide used in the present invention can have any composition ratio, and may be pure silver chloride, pure silver embodiment, or an intermediate composition. It may contain a trace amount of silver iodide.

Silver chlorobromide emulsions having a silver bromide content of 10 mol % or more are preferably used in the present invention. To obtain an emulsion with sufficient sensitivity without increasing fog, the silver bromide content should be 30
Although it is preferable to use mol% or more, if rapidity is required, it may be preferable to use 20 mol% or less or 10 mol% or less.

In a system using the technology of the present invention, when particularly rapid speed is required, the silver bromide content is 3 mol% or less, more preferably 1
It is more preferable to use silver chloride which does not substantially contain silver bromide in an amount of mol % or less.

Reducing the silver bromide content not only improves the speed of development, but also reduces the equilibrium accumulation amount in the developing solution, which is determined by the relationship with the replenishment amount, when a photosensitive material containing silver bromide is run in a processing solution. Bromine ions will be present in low concentrations,
This is preferable because the rapid developability of the developer itself can be set high.

In order to obtain a light-sensitive material that is less prone to fog and exhibits stable gradations using the technique of the present invention, it is desirable to further increase the silver bromide content of the emulsion, preferably 50 mol% or more, and even higher. If it is 65 mol% or more, a very stable emulsion can be obtained.
Preferably, if the silver bromide content exceeds 95 mol%, the rapid developability will decrease by 1, but it can be recovered by using a development accelerator (for example, 3-pyrazolidones, thioethers, hydrazines, etc.), resulting in high sensitivity. Photosensitive materials with stable storage and processability are useful in this field.

The developability of silver halide grains is determined not only by the halogen composition of the entire grain, but also by the halogen distribution within the grain.

Therefore, in the present invention, the silver halide emulsion can have a distribution or structure regarding the halogen composition in its grains. Typical examples thereof are core-shell type or double 17I-shaped particles in which the interior and surface layers of the particles have different halogen compositions.

In such particles, the shape of the core and the overall shape of the shell may be the same or different. Specifically, the core may have a cubic shape and the shelled particle may have a cubic shape, or the core may have an octahedral shape and the shelled particle may have a cubic shape. be. Furthermore, although the core portion is a clearly regular particle, the shape of the shelled particle may be slightly distorted. Furthermore, instead of a simple double structure, it is possible to have a triple structure or more than one structure, or to apply a thin layer of silver halide having a different composition to the surface of the core-shell double structure grain.

In order to have a side channel inside a particle, it is possible to create a particle having not only the enveloping structure as described above but also a so-called bonding structure. The crystal to be joined can have a composition different from that of the crystal serving as the post, and can be formed by joining to an edge, a part of a corner, or a surface of the host crystal. Such a bonded crystal can be formed even if the host crystal is uniform in halogen composition or has a structure such as a core-shell type. Host particles having these structures may be, for example, core-shell type particles in which the core part has a high silver bromide content and the shell part has a low silver bromide content, or vice versa. The particles having a bonded structure themselves may be particles in which the host crystal has a high silver bromide content and the bonded crystal has a relatively low silver bromide content, or vice versa.

In addition, the boundaries between particles with different halogen compositions having these horizontal paths may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to composition differences, or may be actively continuous boundaries. It may also be one with some structural changes.

In the present invention, an emulsion consisting of the above-mentioned core-shell grains or bonded grains having some kind of structure is preferably used, rather than one having a uniform halogen composition within the grains. In particular, grains having a halogen composition in which the silver bromide content is lower on the grain surface than on the inside of the grain are more preferably used. A typical example is a core-shell emulsion in which the core contains a higher content of silver bromide than the shell. Constituent molar ratio of core part and shell part is 0:100
Any ratio between ~100:0 and 100:0 can be used, but in order to make it clearly different from uniform-yokomichi particles, the ratio should be 3:9.
When the shell portion is formed by so-called halogen conversion which takes advantage of the difference in solubility depending on the halogen species of silver halide, it is preferable to have a ratio between 7 and 98:2. It is preferable that the ratio is less than 98:2, and it is particularly preferable that it is less than 99:1.However, it is actually difficult to uniformly cover the particle surface by halogen conversion, and some corners and edges For example, in Ostwald ripening, the halogen distribution of such halogen-converted particles, which tend to adhere unevenly to particles, becomes uniform, but even particles whose distribution becomes uniform in this way still retain the shape immediately after halogen conversion. Even grains can be used as the emulsion of the present invention if they are mainly surrounded by (100) planes.

When core-shell type silver halide grains are used in a system using the technology of the present invention, a more preferable core to shell ratio is between 5:95 and 95:5, and still more preferably 7: It is between 93 and 90:10. Most preferred is 11)1 of 15:85 to 80:20.

The difference in silver bromide content between the core part and the shell part varies depending on the constituent molar ratio of the core part and the shell part, but it is preferably 3 mol % or more and 95 mol % or less.

More preferably, it is 5 mol% or more and 80 mol% or less. Most preferably it is 10 mol% or more and 70 mol% or less. If the silver bromide content is not much different between the core and shell,
It is not substantially different from particles with a uniform structure, but if the composition difference is too large, it tends to cause pressure resistance and other performance problems, which is undesirable. It is preferable that the closer the composition ratio is to O:100 or 100:O, the larger the composition difference is, and the closer the composition ratio is to 50:50, the smaller the composition difference is.

The shape of the silver chlorobromide used in the present invention may be a cube, a rectangular parallelepiped, or a tetradecahedron as long as it is surrounded by (100) planes, or may have other shapes. In particular, in the case of bonded grains, the host crystal Although bonded crystals are produced uniformly on the corners, edges, or faces of Furthermore, bonded particles having a shape similar to those mentioned above are preferably used. Cubic particles are particularly preferably used.

Average grain size of the silver halide emulsion used in the present invention (
The average diameter of the equivalent sphere in terms of volume is 2μ or less, preferably 0.1μ or more, particularly preferably 1.4μ or less, 0.15
μ or more.

The narrower the particle size distribution, the better, and monodisperse emulsions are preferred. In particular, monodisperse emulsions with regular shapes are preferred for the present invention.0 Particle number or weight is ±20% of the average particle size.
An emulsion in which 85% or more of the total grains are contained within the grains, and especially an emulsion in which 90% or more is contained, is preferable.Even in the case of such a monodisperse emulsion, halogens having some structure as described above are particularly preferred. Emulsions consisting of silver oxide grains are preferred.

Furthermore, preferable results can be obtained by mixing two or more of such monodisperse emulsions, particularly cubic or tetradecahedral monodisperse emulsions, or by coating them in a multilayered manner.

When using a mixture of two or more types of monodispersed emulsions, it is preferable to mix them at a mixing ratio of 5% to 95% in terms of silver.The average grain size of the emulsions to be mixed is in terms of wood grain. It is preferable that they differ from each other by 1:1° or more and 1:8 or less, and more preferably 1:1.2 or more and 1:6 or less.

When two types of monodispersed emulsions are mixed, the mixing ratio should be 0.05:0.95 to 0.95 in terms of silver, as described above.
It is preferable to use a ratio between 95:0.05 and more preferably between 0.1:0.9 and 0.9:0°1.

The silver chlorobromide emulsion used in the present invention is P, Glaf-k i
Chirnie et Phys-i by d e s
que Photograpl] 1 que (P -
aul Monte 1, 1967), G.

Written by F. Durfin PhotographicEmu
lsion Chemistry (Fo-cal
Press, 1966. N.V.L.

Written by Zelil<man eshi al Makin
gand Coating Photograp-
hic Emulsion (Focal Pre-e
F using the method described in
It can be made by I. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, but the acidic method is particularly preferred.The method for reacting the soluble silver salt and the soluble halogen salt includes a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. In order to obtain the monodisperse particles of the present invention, it is also possible to use a method (so-called back-mixing method) in which particles are formed under the condition of excess silver ions, preferably a simultaneous mixing method. As one form of the simultaneous mixing method, a method in which the concentration of silver ions in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrold double diet method can also be used. According to this method, it is possible to obtain a monodisperse silver halide emulsion with a regular crystal shape and a narrow grain size distribution suitable for the present invention. It is desirable to prepare based on the method.

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

In particular, the iridium salt or its complex salt is preferably 10-9-10' mol per mol, more preferably 10
-8 to 10-5 mol 1 mol is used. This is compared to emulsions prepared without using iridium salts or their complex salts.
It is particularly useful in obtaining rapid developability and stability when exposure is performed at high or low illuminance outside the appropriate exposure illuminance range.

Known silver halide solvents (for example, ammonia, potassium thiocyanate, or U.S. Pat.
No., JP-A-53-144319, JP-A-54-100
When physical ripening is performed in the presence of 1,000-onythyl compounds and 1,000-on compounds described in No. 717 or JP-A No. 54-155828, etc., monodisperse halogenated compounds having a regular crystal shape and a narrow particle size distribution are produced. A silver emulsion is obtained and is preferred.

To remove soluble salts from the emulsion after physical ripening, washing with water, flocculation sedimentation, ultrafiltration, or the like can be used.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. That is, active gelatin and compounds containing sulfur that can react with silver ions! 1lJ(
For example, sulfur sensitization using thiosulfates, thiourea compounds, mercapto compounds, rhodanine compounds, etc.), reducing substances (such as stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc.) and reduction sensitization using metal compounds (e.g. gold complex salts, p
The monodisperse salt odor of the present invention can be used alone or in combination with a noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as t, Ir, Pd, Rh, Fe, etc. For silveride emulsions, sulfur sensitization or selenium sensitization is preferably used, and during this sensitization, it is also preferable to include a hydroxyazaindene compound.

In the present invention, the use of spectral sensitizing dyes is important. As the spectral sensitizing dyes used in the present invention, cyanine dyes, merocyanine dyes, composite merocyanine dyes, etc. are used.

In addition, complex cyanine dyes, poropolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used. As cyanine dyes, simple cyanine dyes, carbocyanine dyes, and dicarbocyanine dyes are preferably used. These cyanine dyes can be represented by the following formula.

-Maximum (1) In the formula, L represents a methine group or a substituted methine group, R1 and R2 each represent an alkyl group or a substituted alkyl group, and Zl and Z2 each form a nitrogen-containing 5R to 6-membered heterocyclic nucleus. X represents an anion, n represents a numerical value of 1.3 or 5, nl and R2 are each 0 or 1, and when n=5, n
Both l and R2 are 0, and when n=3, either nl or R2 is 0. 0m represents O or 1, but is 0 when forming an inner salt. Further, when n is 5, the rings may be connected to each other to form a substituted or unsubstituted 5- or 6-membered ring.

- The cyanine dye represented by maximum (1) will be explained in detail below.

Examples of the substituents of the substituted methine group represented by (2) include lower alkyl groups (eg, methyl group, ethyl group, etc.) and aralkyl groups (eg, benzyl group, phenethyl group, etc.).

The alkyl residue represented by R1 and R2 may be linear, branched, or cyclic, and the number of carbon atoms is not limited, but is preferably 1 to 8, particularly 1 to 4.
is particularly preferred, and examples of the substituents of the substituted alkyl group include a sulfonic acid group, a carboxylic acid group, a hydroxyl group, an alkoxy group, an acyloxy group, and an aryl group (eg, a phenyl group, a substituted phenyl group, etc.). These groups may be bonded to the alkyl group alone or in combination of two or more. In addition, sulfonic acid groups and carboxylic acid groups may form salts with alkali metal ions or quaternary ions of organic amines. Here, a combination of two or more means that each of these groups independently forms a salt with an alkali metal ion or a quaternary ion of an organic amine. Examples of the latter include sulfoalkoxyalkyl groups, sulfoalkoxyalkoxyalkyl groups, carboxyalkoxyalkyl groups, and sulfophenylalkyl groups, including cases where the group is bonded to a group and cases where these groups are linked and bonded to an alkyl group. Can be done.

Specific examples of R1 and R2 are methyl group, ethyl group, n-propyl group, n-butyl group, vinylmethyl group,
2-hydroxyethyl group, 4-hydroxybutyl group, 2
-acetoxyethyl group, 3-acetoxypropyl group, 2
-methoxyethyl group, 4-methoxybutyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-(
2-carboxyethoxy)ethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-
Sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2-3-sulfopropoxy)ethyl group, 2-acetoxy-3-sulfopropyl group, 3-methoxy-2-(
3-sulfopropoxy)propyl group, 2- (2-(3
-sulfopropoxy)ethoxy]ethyl group, 2-hydroxy-3-(3'-sulfopropoxy)propyl group, and the like.

Specific examples of the nitrogen-containing heterocyclic nucleus formed by Zl or I2 include oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, pyridine nucleus, oxazoline nucleus,
Examples include a thiazoline nucleus, a selenazoline nucleus, an imidacilline nucleus, and those condensed with a benzene ring, a naphthalene ring, or a saturated or unsaturated atom ring thereof, and these nitrogen-containing heterocycles may further contain substituents. (For example, alkyl groups, trifluoromethyl groups, alkoxycarbonyl groups, cyano groups, carboxylic acid groups, carbamoyl groups, alkoxy groups, aryl groups, acyl groups, hydroxyl groups,
halogen atoms, etc.) may be bonded.

The anion represented by X is CQ-1Br″″1
+-S 04''''-1N 03-CQ 04-, etc. can be mentioned.

Specific examples of cyanine dyes represented by the formula -m are shown below.

(V-1) (V-2) (V-3) (V-4) C21-15 (CI42) 3S03″″ (V-5) (V-6) (V-7>(V-S> ( V-9) (V-10) (V-11) (Xl-1 to V-12 CHI-151:e:c:〉
〉 (V-171 (V-18) (■-+9) (V-20+ (CO2)3So3H-NEta (V-21) (V-22) (V-23) (V-211) (V-25+ ( CH, ), So, H-NEt.

(V-26) (CH2)4So,H-NEt3 (V-27) (CH,)3So3K L and F'I2) 3. jLJ, ii’NIJt.

(V-29) (V-30) (V-313 (V-32) 5tJ%tEt, SOi, - (V-331 (V-34) (v-35) SO, - (V-36) "U3 So H-Nk, t3 (V-37
> (CH2) 4So, H-NEt.

(v-38) (V-39) (CM,), So, H-NEt.

(V-40) (C)I2) 4So, H-NF, t.

(V-411 (V-43) (V-44) (V-45) (v-46)- (V-47) (V-48) (L:H2) zbIJ2 G,) I.

(V-l'Jl (V~50) c~'-51) (V-'52) (shiI''12)3δUa C2H3 (v-53
) (V-54) (V-551 (CH,), 5o3H-NEt.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene side channel.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc. can be incorporated.

The present invention includes a biroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a virol nucleus, a thiazole nucleus, an oxazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, an alicyclic hydrocarbon ring, and an aromatic ring. Spectral enhancement dyes other than those described above that incorporate a nucleus of fused hydrocarbon rings may also be used.
1 Useful spectral enhancing dyes include, for example, German Patent No. 929,080, U.S. Pat. No. 2,231.6
No. 58, No. 2.493,748, No. 2,503.
776, same No. 2,519,001, same (No. 2,
No. 912.329, No. 3,656,959, No. 3
．． No. 672.897, No. 3,694.217, No. 4.025,349, No. 4.046,572, British Patent No. 1,242゜588, Japanese Patent Publication No. 1403-1973
Examples include those described in No. 0, No. 52-24844, and the like.

In the present invention, among the above dyes, those having a benzothiazole nucleus or a benzoxazole nucleus are preferable, such as simple cyanine dyes having a benzothiazole nucleus, carbocyanine dyes having a benzoxazole nucleus, and dicarbocyanine dyes having a benzothiazole nucleus. Dyes are particularly preferred.

Usually, in order to spectral sensitize a silver halide emulsion, a method is used in which grains are completely formed and then a spectral sensitizing dye is adsorbed onto the surface of the grains. On the other hand, U.S. Patent No. 2,735,766 discloses a method of adding a merocyanine dye during precipitation of silver halide grains, which is believed to reduce the amount of dye that is not adsorbed. Are listed. Also, JP-A-55-26
No. 589 discloses a method in which a spectral sensitizing dye is added and adsorbed during addition of an aqueous silver salt solution and a halogen salt aqueous solution to form silver halide crystal grains. In this way, the spectral sensitizing dye may be added during the formation of silver halide crystal grains, after the formation is completed, or even before the formation begins.

Specifically, "before the start of grain formation" means that a spectral sensitizing dye is introduced into the reaction vessel before starting the reaction to form silver halide crystals, and "during grain formation" means that the spectral sensitizing dye is introduced into the reaction vessel before starting the reaction to form silver halide crystals. 10 The silver halide emulsion of the present invention can be added and adsorbed after the completion of grain formation. Although chemical sensitization is performed, the addition of a spectral sensitizing dye after the completion of grain formation may be performed before the start of such chemical sensitization, during chemical sensitization, or after the completion of chemical sensitization. In the present invention, the above-mentioned spectral sensitizing dye may be added at any time after the formation of silver halide grains is substantially completed. It is preferable to add and adsorb it in at least one of the above steps, but it is also possible to add it over two or more steps or in parts, and even in one step, it can be added intensively in a short period of time. It may also be added continuously over time, or several such addition methods may be combined.

The spectral sensitizing dye to be added may be directly crystalline or 15)
Although it may be added as a powder, it is preferable to dissolve or disperse it by some method before adding it.To dissolve it, use a water-soluble solvent such as an alcohol having 1 to 3 carbon atoms, acetone, pyridine, or methyl cellosolve. Alternatively, a mixed solvent thereof may be used, or a surfactant may be used to perform micelle dispersion or other dispersion.

The amount of spectral sensitizing dye added depends on the purpose of spectral sensitization and the content of the silver halide emulsion, but it is usually from 1X10' mol to 1X10'2 mol per 1 mol of silver halide.
moles, more preferably 1×10 moles to 5×10″″
3 moles are added.

The spectral sensitizing dye used in the present invention may be used alone, but
Two or more types may be used in combination.

Along with the spectral sensitizing dye, it contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer that has no substantial absorption in the visible region but enhances the sensitizing effect of the spectral sensitizing dye. Good too.

In the present invention, aminostilbene compounds substituted with a nitrogen-containing heterocyclic group (for example, U.S. Patent Box 2.933.3
90 and the same No. 3,635,721),
The azaindene compound is useful for reducing the residual color of the carbocyanine dye having an oxazole nucleus and improving the color sensitization of the dicarbocyanine dye having a benzothiazole nucleus or a benzoxazole nucleus, and is particularly preferably used in combination. In particular, hydroxyazaindene compounds also increase color! Preferable for improving S properties.

As the aminostilbene compound preferably used in the present invention, 4,4'-bis(S-triazinylamino)stilbene-2,29-disulfonic acid or 4,4'-
Examples include bis(pyrimidinylamino)stilbene-2,2''-disulfonic acid and alkali metal salts thereof. In these metal compounds, the s-) riazine ring or pyrimidine ring is a substituted or unsubstituted arylamino group,
It is more preferable that one or two positions are substituted with a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkyloxy group, or a hydroxyl group or an amino group. It is more preferable for this moiety to be substituted with a highly water-soluble substituent in order to reduce the amount of water.The highly water-soluble substituent is, for example, a substituent containing a sulfonic acid group or a hydroxyl group.

These compounds are represented by the following general formula (F).

General formula (F) In the formula, D represents a divalent aromatic residue, R12, R13,
R14 and R15 are each a hydrogen atom, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclylthio group, an amine group, an alkylamino group, a cyclohexylamino group, Represents an arylamino group, a heterocyclylamino group, an aralkylamino group, or an aryl group.

Ql and Q2 each represent -N= or -C=, provided that at least one of Ql and Q2 is -N=.

Below, particularly preferably used in the present invention (1?
-1) (F-2+ CF-31 (F-ll) 1 F -5) (F-G) (F-71 (F-8) (F-9> CF-10) (F-+t) (F -121 (F-131 (F-141 (F-151 (F-16) (1"-171 (F-181 (F-19) (F -201 (F-211 (F-221 f F-2111 The silver halide emulsion of the present invention has properties that prevent the occurrence of fog and stabilize photographic performance during the manufacturing process of photographic optical materials, during storage before development, or during development. The following compounds can be added for the purpose of increasing the mercapto compound: first of all, heterocyclic mercapto compounds, such as mercaptothiadiazoles, mercaptotetrazoles, mercaptobenzimidazoles,
mercap-1-benzothiazoles, mercaptopyrimidines, mercaptothiazoles, etc.; secondly, the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfurine group; and thirdly, azoles such as benzo Thiazolium salts, nitroindazoles, l-lyazoles, benzotriazoles, benzimidazoles (
fourthly, thioketo compounds such as oxazolidinethione, and fifthly azaindenes such as tetraazaindenes, etc.
Furthermore, there are benzenethiosulfinic acids, benzenesulfinic acids, and the like. In particular, heterocyclic mercabinyl compounds and azaindenes are preferably used in the present invention.

Preferred azaindenes can be selected from compounds represented by the following general formula (ma) or (ntb).

General formula (lla) In the formula, R1, R2, R3 and R4 may be the same or different, and are hydroxyl group, alkyl group, alkenyl group, aryl group, cyano group, ureido group, amino group, halogen atom or hydrogen atom represents one or two hydroxyl groups.

The above alkyl group, alkenyl group, aryl group, ureido group and amine group have the same meanings as those in general formula (Ia) below. Particularly preferred substituents for the alkyl group include an allyl group, an alkoxycarbonyl group, a carbamoyl group, a cyan group, an amino group, and a sulfonamide group.

Furthermore, I'L3 and R4 may be linked to each other to form a 5-6R saturated or unsaturated ring.

General formula (llllb) In the formula, R1, R2 and R3 are R1 of the general formula (ma),
It has the same meaning as R2, but at least one does not need to be a hydroxyl group as in the case of general formula (ll[a).

Specific examples of these compounds are listed below.

(11Otori-1) (11Iris-2) (UT-3) (IJJ-5) Preferred mercap T-tetrazole compounds can be selected from compounds represented by the following general formula (1a). .

In the formula, R does not represent an alkyl group, alkenyl group or aryl group, and X represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor.

Examples of the alkali metal atom include a sodium atom and a potassium atom, and examples of the ammonium group include a trimethylammonium chloride group and a dimethylbenzylammonium chloride group. Further, the precursor refers to a group that can form X=H or an alkali metal under alkaline conditions, and represents, for example, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, and the like.

Among the above R, the alkyl group and alkenyl group include unsubstituted and substituted groups, and also include alicyclic groups.

Substituents for substituted alkyl groups include halogen atoms, alkoxy groups, aryl groups, acylamino groups, alkoxycarbonylamino groups, ureido groups, hydroxyl groups, amino groups, heterocyclic groups, acyl groups, sulfamoyl groups, sulfonamide groups, and thioureido groups. group, a carbamoyl group, and furthermore a carboxylic acid group, a sulfonic acid group, or a salt thereof.

The above ureido group, thioureido group, sulfamoyl group, carbamoyl group, and amino group are each unsubstituted,
Examples of aryl groups, including those substituted with N-alkyl and those substituted with N-aryl, include phenyl and substituted phenyl; substituents include alkyl and substituents of the alkyl groups listed above. can be mentioned.

Further, a preferable mercaptothiadiazole compound can be selected from among the compounds represented by the following general formula (Ua).

General formula (■a) In the formula, L represents a divalent linking group, R represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group number, R's alkyl group, alkenyl group, and X represent general formula (Ia) It is synonymous with that of

Specific examples of the divalent linking group represented by the above can be mentioned. n represents 0 or 1, ROlRl,
and R2 each represent a hydrogen atom, an alkyl group, or an aralkyl group. Specific examples thereof are listed below.

S l-1 b 1-1 b (■-1 (■-3) (■-5 (II-6)) In the present invention, irradiation during exposure or printing is prevented. For the purpose of increasing safety against so-called Safely 1-, it lowers sensitivity or worsens latent a @ 1, does not have a negative effect on the photographic characteristics, and reduces quality as residual color after processing. It is particularly preferable to use dyes which do not cause any oxidation, such as those shown below.

In addition to these pyrazolone oxonol dyes, anthraquinone dyes may also be used.

-40'l)- As the pyrazolone oxonol dye, a compound represented by the following general formula (D) is preferably used.

-maximum (D) where R1 and R2 are respectively -COOR5 and -CON-
R3 and R4 each represent a hydrogen atom, an alkyl group or a substituted alkyl group (e.g. methyl group, ethyl group, butyl group, hydroxyethyl group, etc.), and R5
, R6 each represents a hydrogen atom, an alkyl group or a substituted alkyl group (e.g., methyl group, ethyl group, butyl group, hydroxyethyl group, phenethyl group, etc.), an aryl group or a substituted aryl group (e.g., phenyl group, hydroxyphenyl group, etc.) Ql and Q2 each represent an aryl group (e.g. phenyl group, naphthyl group, etc.), Xi
, X2 represents a bond or a 2m linking group, and Yl
, Y2 represents a sulfo group and a carboxyl group, respectively.
LL, L2, L3 each represent a methine group, m
l, m2 is 0.1 or 2, n is 0.1 or 2
, pi and p2 are respectively 0.1.2.3 or 4,
sl and s2 each represent 1 or 2, tl and t2 each represent O or 1, provided that mt, pi,
tl, m2, p2, and t2 never become 0 at the same time.

(D-1) (D-2) (D-3) (D-4) (D-5) (D-6) (D-, 7) CD-8) Photosensitive materials related to Kinoe 1 Da J It is preferable to provide appropriate auxiliary layers such as a silver chloride emulsion layer, a protective layer, an intermediate layer, a filter layer, an I-ration prevention layer, and a back layer.

Binders or retention colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used.

For example, gelatin conductors, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives;
Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinyl bizole, etc. can be used.

In addition to lime-treated gelatin, acid-treated gelatin and 13u11. Sac, Sci, Phot.

Enzyme-treated gelatin as described in Japan, O/I, page 3θ (/2-6) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

The emulsion layer and auxiliary layer of the light-sensitive material according to the present invention may contain various other photographic additives. For example, antifoggants, dye image fading inhibitors, color stain inhibitors, fluorescent whitening agents, antistatic agents, hardeners, surfactants, storm softeners, as described in Research Disclosure Magazine No. 776-3. , wetting agents, ultraviolet absorbers, and the like can be used as appropriate.

In the silver halide photographic material of the present invention, each constituent layer such as an emulsion layer and an auxiliary layer containing various photographic additives as described above may be subjected to corona discharge treatment, flame treatment or ultraviolet irradiation treatment. It is produced by coating on a support coated with a coating, or by coating it on a support via a subbing layer or an intermediate layer. Advantageously used supports include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or with a reflector, such as glass plates. Polyester films such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc.
These supports are appropriately selected depending on the intended use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also US Patent Co.

7, </, 7? According to the method described in / issue, same co, tag/, rri issue 2. Simultaneous coating of two or more layers can also be used.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily, but for example, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are arranged sequentially from the support side, or on the support side. A red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer can be sequentially arranged.

Further, an ultraviolet absorber layer may be provided in a layer adjacent to the support side of the emulsion layer furthest from the support, and if necessary, an ultraviolet absorber layer may be provided in a layer on the opposite side of the support. Particularly in the latter case, it is preferable to provide the uppermost layer with a protective layer consisting essentially of gelatin.

When the present invention 1 is applied to a color photosensitive material for printing, the photosensitive material is exposed through a negative photosensitive material having a color image made of a coupling product, and then subjected to color development processing.

Color development geography is carried out by conventional color development methods.

Photographic processing of light-sensitive materials obtained using the technology of the present invention includes, for example, Research Disclosure (Research Disclosure).
ch Disclosure) No. 176, No. 28-3
° as described on page 0 (RD-17643),
Any known method and known treatment liquid can be applied. This photographic processing may be a photographic process that forms a silver image if a color image is finally obtained, or a photographic process that directly forms a dye image.The processing temperature is normal. Temperatures between 18 and 50°C are preferred, but temperatures below 18°C or above 50°C may also be used.

There are no particular restrictions on the color photo processing method, and various methods can be applied.For example, representative methods include:
A method in which color development and bleach-fixing are performed after exposure, followed by washing and stabilization as necessary.A method in which color development, bleaching and fixing are performed separately after exposure, and further washing and stabilization are performed as necessary. After exposure, the film is developed with a developer containing a black and white developing agent, and then exposed to -like light.
Color development and bleach-fixing are carried out, followed by washing and stabilization as necessary, or after exposure, development is carried out with a developer containing a black and white developing agent, and further containing a fogging agent (for example, sodium borohydride). There is a method in which the image is developed with a color developing solution and then subjected to bleach-fixing treatment, followed by further washing with water and stabilization treatment as required.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developing agents include aminophenol and p-phenylenediamine derivatives. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)1-luene D-44-(N- Ethyl-N-(β-hydroxyethyl)aminecoaniline D-52-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-6N-ethyl-N-(β-methanesulfone) (amidoethyl)-3-methyl-4-aminoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3- Methyl-N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-butoxyshetylaniline These p-phinidine diamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, p-1-luenesulfate, etc. The above compounds include rice 1.1.
I Patent No. 2,193.015, I Patent No. 2,552°241, I Patent No. 2,566.271, I Patent No. 2,592.364,
It is described in the same No. 3,656,950, the same No. 3゜698.525, etc. The amount of the aromatic primary amine color developing agent used is in a concentration of about 0.1 g to about 20 g, more preferably about 0.5 g to about log per developer solution IQ.

As is well known, the color developer used in the present invention may contain hydroxylamines.

Hydroxylamines can be used in the form of free amines in color developers, but are more commonly used in the form of water-soluble acid salts.

Common examples of such salts are sulfates, oxalates,
Salts include arsenic salts, phosphates, carbonates, acetates, and others. The hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxylamines may be substituted with an alkyl group.

The amount of hydroxylamine added is 10 per color developer IQ.
g or less, more preferably 5 g or less.
If the stability of the color developing solution is to be maintained, it is preferable that the amount added be small.

In addition, as preservatives, sulfites such as sodium sulfite, potassium sulfite, ffi sodium sulfite, potassium bisulfite, thorium metasulfite, potassium metasulfite, etc.
It is preferable to contain a carbonyl sulfite adduct, and the amount of these added is preferably 20 g or less per color developer IQ, more preferably 5 g or less, and the smaller the amount is, the more preferred is that the stability of the color developer is maintained. .

As the perturbation agent, JP-A-52-49828, JP-A-56-47038, JP-A-56-32140, JP-A-59-
160142 and U.S. Pat. No. 3,746.544; U.S. Pat. No. 3,615
．． 503 and British Patent No. 1,306,176; α-aminocarbonyl compounds described in JP-A-52-143020 and JP-A-53-89425; JP-A-57-44148 and JP-A-57-53
Various gold RMs described in No. 749, etc.; JP-A-52-1027
Various saccharides described in No. 27; hydroxamic acids described in No. 52-27638; α, α described in No. 59-160141
-Dicarbonyl compounds; Salicylic acid M described in No. 59-180588; Alkanolamines as described in No. 54-3532; Poly(alkylene imines) as described in No. 56-94349; Gluconic acid as described in No. 56-75647 Derivatives etc. can be mentioned. These preservatives may be used for 2WA or more if necessary, especially 4,5-
Additions such as dihydroxy-m-benzenedisulfonic acid, poly(ethyleneimine) and triethanolamine are preferred.

The pH of the color developer used in the present invention is preferably 9.
N12, more preferably 9 to 11, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffering agents. Examples of the buffering agents include carbonate, phosphate, povate, tetraporate, hydroxybenzoate, glycine salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have low solubility and pl-19,
GTR performance is affected in the high pH range of 0 or more, and even when added to color developing solutions, it has an adverse effect on photographic processing performance (occurrence of fog)
It is particularly preferable to use these buffers because they have the advantages of being free from oxidation and being inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate, lithium (7I; potassium tetraborate, 0-hydroxyan, se, aromatic acid), lithium
salicylic acid) Potassium 0-hydroxybenzoate, 7 g of 5-sulfo-2-hydroxybenzoate, sodium frate (5-sulfo→)°sodium lycylate), potassium 5-sulfo-2-hydroxybenzoate (5-sulfo-2-hydroxybenzoate) potassium salicylate), etc. However, it is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mol/Q or more, particularly 0.1 mol/[~0.4
Particularly preferred is mol/J2.

(a) It is preferable to use various chelating agents in the color developing solution as an anti-settling agent for calcium or magnesium or to improve the stability of the color developing solution.

As the chelating agent, organic acid compounds are preferable, such as aminopolycarboxylic acids described in Japanese Patent Publication Nos. 48-030496 and 44-30232, and JP-A-56-9734.
No. 7, Special Publication No. 56-39359 and West German Patent No. 2,
Organic phosphonic acids described in No. 227,639, JP-A-52
-102726, 53-42730, 54-1
No. 21127, No. 55-126241 and No. 55-
Examples include phosphonocarboxylic acids described in JP-A-58-195845, JP-A-58-203440, and JP-B-Sho 53-40900. Specific examples are shown below, but the invention is not limited to these.

・Nitrilotriacetic acid ・Diethyleneaminopentaacetic acid ・Ethylenediaminetetraacetic acid ・)~lyethylenetetraminehexaacetic acid ・N,N,N-trimethylenephosphonic acid ・Ethylenediamine-N,N,N',N''-tetramethylenephosphonic acid ・1,3-diamino-2-propanol-tetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotriacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, hydroxyethylenediamine triacetic acid Acetic acid, ethylenediamineol-1-hydroxyphenylacetic acid, 2-boshoptane-1,2,4-tricarboxylic acid, 1-hydroxyethane-1,1-diphosphonic acid, N,
N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid These chelating agents may be used in combination of 2 m or more if necessary.The amount of these chelating agents added depends on the amount of metal in the color developer. The amount may be sufficient as long as it is sufficient to chain ions, for example, about 0.1 g to Log per IQ.

Any development accelerator can be added to the color developing solution if necessary.

As a development accelerator, in addition to benzyl alcohol, Japanese Patent Publications No. 37-16088, No. 37-5987, and No. 38-7
Thioether compounds described in No. 826, No. 44-12380, No. 45-9019, and U.S. Patent No. 3,813,247:
p-phinidine diamine compounds described in No. 0-15554, JP-A-50-137726, JP-B No. 44-30
No. 074, JP-A-56-156826 and JP-A No. 52-
Quaternary ammonium salts described in U.S. Pat. No. 43429, etc.: p-aminophenols described in U.S. Pat.
No. 94.903, No. 3,128゜182-, No. 4,2
No. 30,796, No. 3,253.919, Special Publication No. 1977
-11431, U.S. Patent No. 2,482.546, No. 2
, 596.926 and 3,582.346, etc.; Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, U.S. Patent No. 3,128.183,
Polyalkylene oxides described in Japanese Patent Publication Nos. 41-11431, 42-23883, U.S. Patent No. 3,532.501, etc., other 1-phenyl-3-pyrazolidones, hydrazines, meso ion type compounds, thione type compounds, imidazole etc. can be added as necessary. Especially thioether compounds and 1-phenyl-
3-pyrazolidones are preferred.

In the present invention, a pressureless antifoggant can be added to the color developing solution depending on the tV requirement. As antifoggants, alkali metal halides such as hypotassium, sodium bromide, and potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitroindazole, 5-nitroindazole, 5-methylbenzotriazole, 5-nitrobenzo1-riazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole and hydroxyazaindolizine; and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, and 2-mercapto-benzothiazole. , adenine, and even mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. These antifoggants may be eluted from the silver halide color photographic light-sensitive material during processing and may accumulate in the color developing solution, but from the viewpoint of reducing the amount of emissions, it is preferable that the amount of these accumulated is small. .

The color developing solution of the present invention preferably contains a fluorescent whitening agent.
, 2'-disulfostilbene type compounds are preferred, and the amount added is O~5g/l! Preferably it is 0.1 g to 2 g/Q.

Furthermore, various surfactants such as alkylphosphonic acids, arylposponic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developing solution in the present invention is 30 to 50°C.
is preferable, and more preferably 33 to 42. The replenishment amount is 30 to 1500 cc, preferably 30 to 600 cc, and more preferably 30 to 30 cc per 1nr of photosensitive material.
It is 0cc. From the viewpoint of reducing the amount of waste liquid, it is preferable that the amount of these replenishments be small.

Ferric ion salts are generally used as the bleaching agent in the bleach solution or bleach-fix solution used in the present invention.

Ferric ion button salt is preferably a precious wood made of ferric ion and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or their salts. Salts of polycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, and water-soluble amines are preferred; the alkali metals include 1 to 1, potassium, lithium, etc., and the water-soluble amines include methylamine, diethylamine, and 1. -Alkylamines such as ethylamine and butylamine, alicyclic amines such as cyclohexylamine, alkylamines such as aniline and m-toluidine, and heterocyclic amines such as pyridine, morpholine and piperidine.

Typical examples of cleaning agents such as aminopolycarboxylic acids, aminopolyposponic acids, or salts thereof include: - ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenethiaminthi 1-UI! il: Acid diammonium salt, ethylenediaminetetraacetate tetra(trimethylammonium) salt, ethylenethiaminthi I-acetate tetrapotassium salt, ethylenethiaminthi 1-raacetic acid tetrasodium salt, ethylenethiaminthi 1-raacetic acid trisodium salt, Diethylene 1-liaminebentaacetic acid, diegulene 1-liaminebentaacetic acid pentasodium salt, ethylenediamine-N-(β-oxyethyl)-N,
N', N"-1・Liacetic acid・ethylenediamine-N-(β-oxyethyl)-N,
N'-N' -1-Triacetic acid trisodium salt/ethylenediamine-N-(β-oxyethyl)-N,
N', N"-1・1-lyroacetic acid 1~lyammonium salt・propylene cyaminthi 1~acetic acid・propylene cyaminch 1~lyroacetic acid disodium salt・21-lyro1-lyoacetic acid・21~lyrotriacetic acid 1 ~ Linalium salt, cyclohexanediaminetetraacetic acid, cyclohexanediaminetetra I!il: Acid cinna 1-
Lium salt, iminodiacetic acid, dihydroxyethylglycine, ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, phenylene thiamine 1~
Acetic acid/1,3-diaminopropanol-N,N,N'.

N'-tetramethylenephosphonic acid/ethylenediamine-N,N,N',N'-tetramethylenebosphonic acid/1,3-propylenediamine-N,N,N'.

Nl, -tetramethylenephosphonic acid and the like can be mentioned, but of course the compound is not limited to these compounds.

Ferric ion S11 salt may be used in the form of a complex salt,
Ferric salts, such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium viate, ferric phosphate, etc., and aminopolycarboxylic acid, aminopolyphosic acid, 7I; A ferric ion complex salt may be formed in a solution using a chelating agent such as a carboxylic acid. When used in the form of a complex salt, one type of complex salt may be used, or two types of complex salts may be used.
More than one type of complex salt may be used.On the other hand, when forming a complex salt in a solution using a ferric salt and a chelating agent, one or more types of ferric salts may be used. -1- You may use one type or two or more types of agents.

Further, in either case, the chelating agent may be used in excess of the amount necessary to form the ferric ion salt.

Among the iron complex salts, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/a, preferably 0.05 to 0.50 mol/a.

Further, a bleach accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleach accelerators include U.S. Pat. No. 3,893.858, West German Pat.
JP 53-32736, JP 53-57831, JP 53-37418, JP 53-65732, JP 53-
No. 72623, No. 53-95630, No. 53-956
No. 31, No. 53-104232, No. 53-12442
No. 4, No. 53-141623, No. 53-28426, Research Disclosure No. Nα17129 (1
Compounds having a mercapto group or disulfide group described in JP-A No. 50-140129; Japanese Patent Publication No. 45-8506;
Thiourea derivatives described in JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-58-1
Iodide described in No. 6235; West German Patent No. 966.41
0, polyethylene oxides described in JP-A No. 2,748,430; polyamine compounds described in JP-A No. 45-8836; and others JP-A-49-42434, JP-A-49-
No. 59644.

No. 53-94927, No. 54-35727, No. 55
Examples include the compounds described in No. 26506 and No. 58-163940, as well as iodine and bromide ions.

Among them, compounds having a mercapto group or a disulfide group are preferable in terms of the ra1 point where they have a large promoting effect, and are particularly preferred in U.S. Pat.
．． No. 812, - Compounds described in JP-A No. 53-95630 are preferred.

Additionally, the bleach or bleach-fix solutions of the invention may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. iodide). ammonium) rehalogenating agent,
Boric acid, porax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, as necessary.
pH of phosphorous acid, phosphoric acid, sodium phosphate, citric acid, 1-lium citrate, tartaric acid, etc.) One or more types of inorganic acids and organic acids having JE binding ability, and their alkali metal or ammonium salts; Corrosion inhibitors such as ammonium nitrate, guanidine, etc. can be added.

The fixing agent used in the bleach-fixing solution or fixing solution of the present invention is:
Known fixing agents, i.e., thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as thorium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid, 3,6-cythio-1,8-octanediol, etc. These are water-soluble silver halide dissolving agents such as thioether compounds and thioureas, and these can be used alone or in combination of two or more. In addition, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used.In the present invention, thiosulfate, Particularly preferred is ammonium thiosulfate.

The amount of fixing agent per IQ is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fix solution or fix solution in the present invention is 3.
-10 is preferable, and 4-9 is especially preferable, pH
If it is lower than this, the desilvering property is improved, but the storage stability of the solution is deteriorated and the leukolysis of the cyan dye during processing is accelerated.

On the other hand, if the pH is higher than this, desilvering is delayed and staining is likely to occur.

To prepare p I (1), add hydrochloric acid, sulfuric acid, nitric acid, acetic acid (glacial acetic acid), bicarbonate, ammonia, potassium hydroxide, arsenic hydroxide, sodium carbonate, Potassium carbonate etc. can be added.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer of the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.)
Contains sulfite ion-releasing compounds such as. These compounds preferably contain about 0.02 to 0.50 mol/Q gold in terms of sulfite ion, more preferably 0.0 mol/Q gold.
It is 4 to 0.40 mol/Q.

As a preservative, sulfite is generally added, but ascorbic acid, carbonyl bisulfite, carbonyl compound, etc. may also be added.

Furthermore, buffering agents, optical brighteners, chelating agents, anti-piping agents, etc. may be added as necessary.

Next, the water washing process of the present invention will be explained. In the present invention, instead of the usual "water washing process", a simple treatment method such as not providing a substantial water washing process and only performing a so-called "stabilization process" is used. You can also do it. As described above, the term "water washing treatment" as used in the present invention is used in the broad meaning described above.

The amount of water for washing in the present invention is determined by the number of baths in multi-stage countercurrent washing and the amount of water for photosensitive material]
Although it is difficult to specify the concentration because it differs depending on the pre-bath component brought in, in the present invention, the concentration of the pre-bath component having bleach-fixing ability in the final washing bath is preferably 5XIO' or less, and more preferably 2X10-2 or less. Preferably 0 For example, in the case of 3-tank countercurrent water washing, about 1000 cc per 1M of photosensitive material
It is preferable to use more than 1,000 cc or more per 1nr of photosensitive material in the case of water-saving treatment.

The water washing temperature is 15°C to 45°C, more preferably 20°C to 45°C.
It is 0°C.

In the washing process, for the purpose of preventing precipitation and stabilizing the washing water,
Various known compounds may be added, such as chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid; bactericidal agents and anti-spiking agents that prevent the growth of various bacteria, algae, and mold; e.g. , "Journal of Antibacterial and Antifungal Agents" (J, Ant, 1bact, Antifung,
A-genjs) Vol', 11, N(15, p207
~223 (1983) and the compounds described in Hiroshi Horiguchi's "The science of antibacterial and antibacterial", metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or dry loads and A surfactant or the like may be added as necessary to prevent unevenness. Or West's “Fu 1st Graphic.”
Science and Engineering Magazine (Photo,
A compound described in Sci, E-ng, Volume 6, pages 344-359 (1965), etc. may be added.

Furthermore, the method disclosed in Japanese Patent Application No. 61-131.632, in which the washing water is reduced in calcium, magnesium, etc., is also particularly preferably used in the present invention.

Furthermore, chelating agents, bactericides, and anti-piping agents are added to the washing water.
The present invention is particularly effective when the amount of washing water is significantly reduced by multistage countercurrent washing using two or more tanks. It is also particularly effective when carrying out a multi-stage countercurrent stabilization process (so-called stabilization process) as described in JP-A-57-8543 instead of the usual water washing process. In these cases, the bleach-fix components of the final bath should be no more than 5X10-2, preferably 1
It is sufficient if it is not more than ×10−2.

During this stabilization process, various compounds are added for the purpose of stabilizing the image. For example, adjusting the membrane pH (for example, pH 3
to 8) for various [II agents (e.g. porates,
Typical examples include metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and aldehydes such as formalin. can be mentioned. Sonoike, Kill-1 agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic posonic acid, aminopolyphosboxylic acid, phosphonocarboxylic acid, etc.), fungicides (thiazole type, isothiazole type, halogenated phenol, sulfanyl) amides, benzotriazole, etc.), surfactants,
Various additives such as optical brighteners and hardeners may be used.
Two or more of the same or different desired compounds 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 an IBI pH adjusting agent after processing in order to improve image storage stability.

When the amount of washing water is significantly reduced as described above, it is preferable for the purpose of reducing the amount of waste liquid to flow some or all of the overflow liquid of the washing water into the bleach-fixing bath or the fixing bath, which is a prebath.

In this treatment step, during continuous treatment, a constant finish can be obtained by using a replenisher for each treatment solution to prevent fluctuations in the liquid composition. The amount of replenishment is preferably as small as possible, as long as good photographic properties can be maintained, depending on the composition of the processing solution, temperature, processing time, stirring, and other processing conditions for cost reduction.

Each treatment bath is preferably provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, a nitrogen stirrer, an air stirrer, etc., as necessary.

Color photographic processing is a process that uses a color developing solution.
It can be applied to any processing process, such as color paper, color reversal paper, color positive film, color negative film, color reversal film, etc.

Examples of the present invention are shown below. For red sensitive layer? Prepare L formulation as follows.

Add 30 g of lime-treated gelatin to 1000 cc of distilled water, dissolve at 40°C, adjust pi4 to 3.8 with sulfuric acid, and add 6.5 g of sodium chloride and 0.02 g of N,N'-dimethylethylenethiourea. and the temperature was raised to 75°C. A solution of 62.5 g of silver nitrate dissolved in 750 cc of distilled water, 35°0 g of potassium bromide, and 4 ml of sodium chloride.
．． A solution prepared by dissolving 3 g of 5° Occ of distilled water was added to and mixed with the above solution for 40 minutes while maintaining the temperature at 75° C. When the resulting emulsion was observed under an electron microscope, it was found that the average side of the emulsion was about 0.43 μm. Cubic particles with length were formed.

Add 62.5 g of silver nitrate to this emulsion in 5°Occ of distilled water.
and a solution prepared by dissolving 26.3 g of potassium bromide and 8.6 g of sodium chloride in 300 cc of distilled water.
The mixture was added and mixed for 20 minutes at 5°C. When the obtained emulsion was observed under an electron microscope, cubic grains having an average side length of about 0.55 μm were formed. When the grain size distribution of this emulsion was measured, the number of grains was approximately 87.
% (hereinafter this value will be referred to as monodispersity) of the emulsion was a monodisperse emulsion in which the grain size was within ±20% of the average grain size. After washing this emulsion with desalinated water, it was optimally chemically sensitized with mono-lium thiosulfate in the presence of a nucleic acid decomposition product.

This emulsion was designated as A.

Furthermore, by changing the reaction temperature for particle formation, the average side length was reduced to 0.
A similar optimally sulfur-sensitized emulsion was prepared with cubic to dodecahedral grains with 35μ and i-angles removed to form a dodecahedron, and a monodispersity of 92%. This emulsion was designated as B.

For emulsions A and B, exemplified compounds (nr-1), (V
-1), (F-7), and (■-1) were added and used for f history.

An emulsion for a green-sensitive layer was prepared as follows.

Add 30 g of lime-treated gelatin to 1000 cc of distilled water, dissolve at 40°C, adjust the pH to 3.8 with sulfuric acid, and add 6.5 g of sodium chloride and 0.02 g of N,N'-dimethylethylenethiourea. The temperature was raised to 60°C. A solution of 62.5 g of silver nitrate dissolved in 750 cc of distilled water, 26°3 g of potassium bromide, and 8.6 g of sodium chloride.
g dissolved in 500 cc of distilled water was added to and mixed with the above solution for 40 minutes while maintaining the temperature at 60°C. When the obtained emulsion was observed using an electron microscope, it was found that cubic grains having an average side length of about 0.36 μm were formed.

Add 62.5 g of silver nitrate to this emulsion and add 500 cc of distilled water.
A solution prepared by dissolving 35.0 g of potassium bromide and 4.3 g of arsenic salt f in 300 cc of distilled water were added and mixed at 70° C. for 20 minutes. When the obtained emulsion was observed under an electron microscope, it was found that cubic grains having an average side length of about 0.45 μm were formed. When the grain size distribution of this emulsion was measured, the monodispersity was approximately 89.
% monodispersed emulsion. After washing this emulsion with demineralized water,
Optimal chemical sensitization was achieved with sodium thiosulfate in the presence of nucleic acid digests. This emulsion was designated as C.

Furthermore, by changing the reaction temperature for particle formation, the average side length was reduced to 0.
A similar optimally sulfur-sensitized emulsion was prepared with cubic to dodecahedral grains at 30 microns with one corner converging to form a dodecahedron, and a monodispersity of 93%. This emulsion was designated as D.

For emulsions C and D, examples (Hymonium compound (Ill-1>,
(V-26>, (V-42), (1-2) should not be added and used.

Emulsions for blue-sensitive layers were prepared in the following manner.

Add 30g of lime-treated gelatin to 700cc of distilled water,
After dissolving at 40°C, adjust the pi-i to 4.2 with UiE acid, add 8.5 g of salt 1 arsenium and 0.03 g of N,N'-dimethylethylenethiourea, and bring the temperature to 78°C. raised. A solution in which 31.25 g of silver nitrate was dissolved in 750 cc of distilled water and a solution in which 20.8 g of potassium bromide and 0.5 g of sodium chloride were dissolved in 500 cc of distilled water were heated at 78°C.
The mixture was added to the above solution and mixed for 40 minutes while maintaining the temperature. When the obtained emulsion was observed using an electron microscope W1, it was found that the emulsion was approximately 0.5
Tedecahedral particles close to cubes with an average side length of 0μ were formed. In addition to this emulsion, 93.75 g of silver nitrate
and potassium bromide dissolved in 500 cc of distilled water.
2g and 8.1g of sodium chloride in 300cc of distilled water
were added and mixed for 20 minutes at 72°C. When the obtained emulsion was observed under an electron microscope,
Cubic particles were formed with an average side length of about 0.80μ. This emulsion was a monodisperse emulsion with a degree of monodispersity of 90%.

After washing this emulsion with desalinated water, it was optimally sensitized with sodium thio[acid] in the presence of a nucleic acid decomposition product.

This emulsion was designated as E.

Furthermore, by changing the reaction temperature for particle formation, the average side length was approximately 0.
．． A similar emulsion with optimal sulfur sensitization was prepared with 55 micron cubic grains and approximately 90% monodispersity. This emulsion was designated as F.

For emulsions E and F, the exemplified compound (111-1>,
(V-34>, (1-2) was added and used.

An emulsified dispersion for the red-sensitive layer was prepared as follows.

Exemplary compounds of the present invention having an average molecular weight of about 60,000 (15 g of P-57, 10 g of Exemplified Compound (C-1), 1.0 g of Exemplified Compound (X-9), 1'' of (X-10)) , 5g and 1.5g of (X-12), exemplified compound!1m(S-11
), 4 g of (S-16), and 0.0 g of compound (a).
2 g and 30 cc of ethyl acetate were mixed and dissolved at 50°C, and this solution was mixed with 12 cc of 10% sodium dodecylbenzene sulfonate to make 190 c of a 10% gelatin aqueous solution.
c, and an emulsified dispersion was obtained using a homogenizer. This emulsified dispersion was designated as (A).

An emulsified dispersion for the green sensitive layer was prepared as follows.

10 g of the exemplary compound (p-57) with an average molecular weight of about 80,000, 10 g of the exemplary compound (M-15''), 1.2 g of the exemplary compound (A-1), and 1.2 g of the exemplary compound (A-1) of the present invention, each having an average molecular weight of about 80,000. 5 g of Exemplified Compound (S-7), 5 g of (S-16), 4.4 g of Compound (b), and 40 cc of ethyl acetate were mixed and dissolved at 50°C, and this solution was dissolved in 10% dodecyl It was added to 210 cc of a 10% aqueous gelatin solution mixed with sodium benzenesulfonate No. 13 and dispersed using a homogenizer to obtain an emulsified dispersion.This was designated as an emulsion (b).

A milk dispersion for the WF sensitive layer was prepared as follows.

19 g of the exemplary compound (P-57) of the present invention having an average molecular weight of about 50,000, 19 g of the exemplary compound (Y-1),
6.0 g of S-25>, and further 4.3 g of compound (c)
Then, 27 cc of ethyl acetate was mixed and dissolved at 50°C, and this solution was mixed with 8 cc of 10% sodium dodecylbenzenesulfonate to create 180 cc of a 10% gelatin aqueous solution.
and dispersed using a homogenizer to obtain an emulsified dispersion.

This emulsion was designated as (c).

The above emulsions A to F and emulsified dispersions (a) to (c) are used to constitute a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer, respectively, and intermediate layers such as an ultraviolet absorbing layer and a color mixing prevention layer, etc. Safe! I
N was provided to prepare coating samples having the layer structure and compound composition shown in Table 1.

The emulsified dispersions for the ultraviolet absorbing layer and the color mixing prevention layer were also prepared in the same manner as the emulsified dispersions for the emulsion layer described above.

This coating sample contains an exemplary compound (D) for the purpose of preventing irradiation and improving image sharpness.
-1), (D-4), (D-7), and (D-8) were used in combination at coating amounts ranging from 0-002 g/rd to 0.04 g/rd, respectively.

In addition, the following compounds (e) and (f) are used as hardening agents for gelatin.
) was used in combination.

(e) (f) CH2NHCOCH2SO2CH=CI(2CH2NH
COCH2SO2CH=CH2(CH2)2NHCOC
H2SO2CH=CH2CH2NHCOCH2SO2C
A 3:1 mixture of H=CH2 (a) (b) (d) Suh 71'\=ゝ\-n' A comparative emulsion was prepared as follows.

30 g of lime-treated gelatin was added to 1000 cc of distilled water, and after dissolving at 40°C, the pH was adjusted to 3.8 with sulfuric acid, 5 g of thorium chloride was added, and the temperature was raised to 75°C. A solution of 62.5 g of silver nitrate dissolved in 750 cc of distilled water, 30.6 g of potassium bromide, and 6 g of sodium chloride.
．． A solution obtained by dissolving 5 g in 500 cc of distilled water was added to and mixed with the above solution for 40 minutes while maintaining the temperature at 75°C. To this emulsion, a solution of 62.5 g of silver nitrate dissolved in 500 cc of distilled water, 30.6 g of potassium bromide, and 6 g of sodium chloride were added.
．． A solution of 5 g dissolved in 300 cc of distilled water was added and mixed over 20 minutes. When the obtained emulsion was observed under an electron microscope, it was found that octahedral grains having an average diameter equivalent to a sphere of about 0.62 μm were formed.

After washing this emulsion with desalinated water, it was optimally chemically sensitized with sulfur to lithium thiosulfate in the presence of a nucleic acid decomposition product.

This emulsion was designated as G.

Emulsion G contains exemplified compounds (III-1), (V-1>,
(F-7) and (II-1) were added and used.

Similarly, an emulsion containing 70 mol % of silver bromide and consisting of octahedral grains having an average diameter equivalent to one sphere of about 0.52 μm was prepared, and the emulsion was subjected to optimum sulfur sensitization to form Emulsion 1 (emulsion 1).

Emulsion i (includes exemplary compound (Ill-1), (v-26)
), (V-43>, (1-2)) were added and used.

Further, in the same manner, an emulsion containing 80 mol % of silver bromide and consisting of octahedral grains having an average equivalent sphere diameter of about 0.90 μm was prepared and subjected to optimal sulfur sensitization to give Emulsion I.

Emulsion I contains exemplary compounds (Ill-1) and (■-34).
, (1-2) was added and used.

In addition, as an emulsified dispersion for comparison, the above-mentioned emulsified dispersion (
Emulsified dispersions (d), (po), and (f) were prepared by removing exemplified compound (P-57) from a), (b), and (c), respectively.

In addition, from the emulsified dispersion (a), exemplified compound (S-11) and (
S-16) from (b) to exemplified compound (S-7) and (S
-16) and milk fhi dispersion prepared by removing exemplified compound (S-25) from (c), (1 to) and (h), respectively.
, (su).

Coating samples 101 to 106 as shown in Table 2 were prepared by combining these emulsions and emulsified dispersions. Sample 1
01 is the same as the sample shown in Table 1.

Table 2 Emulsions A, B, and C, and the mixing ratio of E and F are all sample 10.
1, and the amount of silver coated was the same for each layer for all samples. The coating amount of the coupler contained in each layer of the emulsion was also made to be the same as that of Sample 101.

For samples 101 to 106, the optical wedge and blue, green,
A 0.1 second white exposure was applied through an optical filter for each red color, and the following processing was performed.

The cyan, magenta, and yellow densities of each processed sample were measured, and the sensitivity was determined from the reciprocal of the exposure amount corresponding to a density of 0.5. The sensitivity of sample 1 for samples 101 and 103
02 is set as 100, and samples 104 and 106 are displayed relative to each other by layer, with sample 105 set as 100. Also,
A coated sample stored at 35° C. and 80% for 21 days was subjected to the same exposure and processing to determine the sensitivity. This sensitivity was expressed as a relative value with the aforementioned sensitivity of each sample as 100. Furthermore, light fastness and dark fastness tests were conducted using the above-mentioned treated samples. When each sample was stored for 6 days at a temperature of 100°C, when stored for 10 days at a temperature of 80°C and at a relative humidity of 72%, and when stored for 6 days in a xenon fade meter with an illuminance of 84,000 lux. For each case, the rate of decrease in concentration from the initial concentration of 1.0 was measured. These results are shown in Table 3.

Punishment 1 壓 Packing plate color present 1 Tortoise 37°C 3 minutes 30 seconds Bleach fixing 33°C 1 minute 30 seconds Washing 24-34°C 3 minutes Drying 70-80°C 1 minute The composition of the external treatment solution is as follows. .

Sahoji Gendai Resui 800cc
Diethylenetriaminepentaacetic acid 1.0g di-lilotriacetic acid 2.0g benzyl alcohol 15-Occ diethylene glycol 10.0cc sodium sulfite
2.0g embodied potassium
1.0g potassium carbonate 30.0
gN-ethyl-N-(β-methanesulponamidoethyl)-3-methyl-4-aminoaniline sulfate 4.5g hydroxylamine sulfate 3.0g optical brightener
ex411, made by Custom Chemical Co., Ltd.) Add 1-0 g of water
1000ccpH (25℃'I
10.25 pages Constant liquid water 400cc Ammonium thiosulfate (70%) 150cc Iron ethylenediaminetetraacetate (LIE) Ammonium 55.0g Disodium ethylenediaminetetraacetate 5.0g Add water 1000ccpH (25℃)
6.70101 is a sample of the present invention, and 102 to 106 are samples for comparison.

As can be seen from the results shown in Table 3, sample 1 of the present invention
Compared to sample 102 which does not contain polymer (P-57), 01 has a sensitivity of 35 with almost no decrease in sensitivity of each layer.
The decrease in sensitivity after storage at 80% °C for 21 days was reduced, which is good. Further, the dark fastness of cyan and magenta color images is improved, and the light fastness of cyan, magenta and yellow color images is also improved. Compared to sample 102, sample 103, in which no high boiling point organic solvent was used, had lower sensitivity in all photosensitive layers than sample 101 of the present invention, and the decrease in sensitivity when stored at 80% at 35° C. was also disadvantageous.

Sample 10 using a silver halide emulsion other than the present invention
4 to 106 have the same relationship as samples 101 to 103 in terms of color image fastness, but compared to the sensitivity relationship of sample 101 to sample 102, the sensitivity decrease due to the use of P-57) is remarkable. The decrease in sensitivity during storage at 80% at 35° C. is not significantly reduced, which is not preferable.

From the above, only Sample 101 of the present invention shows no decrease in sensitivity during coating, little decrease in sensitivity during storage, and has excellent color image preservation properties, using a polymer and a high boiling point organic solvent to preserve color images. The advantage of using silver halide emulsions mainly surrounded by (100) planes has become clear when improving properties.

Example 2 Samples 101 to 106 used in Example 1 were subjected to the following treatment and the same tests as in Example 1 were conducted.
I got similar results.

Tokoro Fox Process Satonori Color Development
33℃ 3 minutes 30 seconds bleach fixing 33℃
Wash with water for 1 minute and 30 seconds 24-34℃
Dry for 3 minutes at 70-80°C for 1 minute The composition of the external treatment liquid is as follows.

Color developer water 800cc diethylene l-liaminepentaacetic acid 1.0g dil-lilotriacetic acid 1.5g benzyl alcohol 15.0cc diethylene glycol 10.0cc sodium sulfite
2.0g embodied potassium
0.5g potassium carbonate 30
．． 0g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g hydroxylamine sulfate 4.0g optical brightener (11hi
tex4 [1, made by Custom Chemical Co., Ltd.] Add 1.0g of water
1000ccpH (25℃)
10. Add 20 ml of violet water 400cc ammonium thiosulfate (70%) 150cc ethylenediaminetetraacetic acid iron (III) ammonium 55.0g disodium ethylenediaminetetraacetate 5.0g water
1000ocpi-1 (25℃
) 6.70 Example 3 Samples 101 to 106 used in Example 1 were subjected to the following treatment and the same tests as in Example 1 were conducted.
I got similar results.

Wataru Shorai Satotaka Hakuho color development
38℃ 1 minute 40 seconds bleach fixing 30~3
4℃, 1 minute 00 second rinse 30-34℃
Rinse for 20 seconds■ 30-34℃
Rinse for 20 seconds ■ 30-34℃ Dry for 20 seconds 70-90℃ 50 seconds (Rinse■
→■ Tank countercurrent system was adopted. ) The composition of each treatment liquid is as follows.

Samonjiyutan Koshikisui 800cc diethylenetriaminepentaacetic acid 1.0g 1-hydroxyethylidene-1゜1-diphosphone a (60%) 2.0g dil.lilotriacetic acid 2.0g benzyl alcohol 16.0cc diethylene glycol
10.0cc sodium sulfite
2.0゜Potassium Bromide 0
．． 5g potassium carbonate 30.0gN
-Ethyl-N-(β-methanesulponamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5g Hydroxylamine sulfate 3.0g Optical brightener (White
ex4B, made by Custom Chemical Co., Ltd.) Add 1.5g of water
1000ccpH (25℃)
10.25" coarse = 1 Namizu 400cc thioMLa ammonium (70%> 200cc sulfite sulfur lithium 20.Og ethylenediaminetetraacetate iron (Ill) ammonium 60.og ethylenediaminetetraacetate disodium 10.0g water added
1000ccpi-1 (25℃)
6.70uZ bene 11-riazole 1.0g ethylenediamine-N,N.

Add N', N'-tetramethyleneposponic acid 0.3g water
1000ccpH (25°C)
7.50 Example 4 Samples 101 to 106 used in Example 1 were subjected to the following treatments and tested in the same manner as in Example 1, and the results shown in Table 4 were obtained.

Department ■Konobu Monsho Time color development
38℃ 1 minute 40 seconds bleach fixing 30~
34℃ 1 minute 00 seconds rinse 30~34℃
Rinse for 20 seconds■ 30-34℃
Rinse for 20 seconds ■ Dry for 20 seconds at 30-34℃ 50 seconds at 70-80℃ (Rinse ■
→■ Tank countercurrent system was adopted. ) The composition of each treatment liquid is as follows.

Saho Niman statue water 800cc diethylenetriamine five vinegar 11ffl 1-”1
-Hydroxyethylidene-1,1-sibosulfonic acid (60%) 2.0g2l~
Lilotriacetic acid 2.0g 1,4-diazabicyclo(2,2゜2)octane 7.5g Potassium bromide 0.5g Potassium carbonate
30.0g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5g hydroxylamine sulfate 4.0g optical brightener (UVIT)
EX-CK (manufactured by Ciba Geigy) Add 1.5g water to 1000ccpH (25℃)
10.
25. Blood pressure base water 400 ■ Ammonium 1,000 sulfate (70%) 200 cc Sodium sulfite 20.0 g Ethylenediaminetetraacetic acid iron acetate III) Ammonium 60.0 g Disodium ethylenediamine tetraacetate 10.0 g Add water to 1000 cc pH (25℃>
7.00 dan 2Δ melon ion exchange water (calcium, magnesium 3pp each
m or less) Even in this process, sample 101 of the present invention is comprehensively superior in sensitivity, storage stability of the coated sample, and color image fastness compared to samples 102 to 106 outside the present invention. The advantages of this configuration are clearly demonstrated.

Example 5 Samples 101 to 106 used in Example 1 were subjected to the following treatment and tested in the same manner as in Example 1.
I got similar results.

Department ■ Engineering Page Yang Sho Bacteria amount color development
Bleach and fix at 33°C for 3 minutes and 30 seconds Wash with water at 33°C for 1 minute and 30 seconds
Dry at 24-34℃ for 3 minutes and 30 seconds °7
The composition of the 1 minute external treatment solution at 0 to 80°C is as follows.

You Bojiri Statue Liquid Water 800cc1
-Hydroxyethylidene-1,1-diphosphonic acid (60%) 2.0g triethanolamine 11.0cc benzyl alcohol 15.0cc diethylene glycol 0.2cc potassium sulfite
1.8g potassium bromide
0.6g potassium carbonate 28.
0g N-ethyl-N-(β-methanesulponamidoethyl)-3-methyl-4-aminoaniline sulfate 4.5g hydroxylamine sulfate 3.0g optical brightener (4,4'
-diaminostilbene type) 0.5g lithium chloride 2.0g water added
1000ccpi-1 (25℃)
10.10 Koshorei liquid water 400cc ammonium 1000 sulfate (70%> 120cc sodium sulfite 18.0g ethylenediaminetetraacetic acid iron III acetate) Ammonium 60.0g ethylenediaminetetraacetic acid disodium 5.0g Add water to 1000cc pl-1 ( 25°
C) 6.70 Example 6 Using the processing solutions used in Examples 1 to 5, 600 cc of each bleach-fix solution and 600 cc of each color developer
A simulated running liquid was prepared by mixing 0 cc of the bleach-fixing liquid and used in place of the bleach-fixing liquid in each processing step. Samples 101 to 106 used in Example 1 were subjected to these treatments, and the same tests as in Example 1 were conducted. In the case of the PI treatment, as in the case of each example, sample 101 of the present invention
The results showed that the sensitivity was high, and the storage stability and color image fastness were excellent.

Example 7 Samples 101 and 104 produced in Example 1 were made in 11 millimeters by replacing the example 1 metal material (P-57) used in the emulsified dispersion with one having a molecular weight of 16,100. They were designated as samples 107 and 108, respectively.

Similarly, samples were prepared in which the molecule ff was replaced with one of 1.29 million, and these samples were designated as samples 109 and 110, respectively.

These samples were subjected to the same tests as in Example 1, and the results shown in Table 5 were obtained. Here, the relative sensitivity immediately after coating is for samples 107 and 109! ? The 15 degrees of C material 101 were expressed as 100, and the sensitivity of sample 104 was expressed as 100 relative to samples 108 and 110.

In Table 5, samples 101, 107, and 109 are samples of the present invention, and samples 104, 108, and 110 are samples that are not of the present invention. It can be seen that only the sample of the present invention exhibits poor sensitivity, storability, and color image fastness at the same time, although the effect is slightly less when the molecular weight is low.

Example 8 For samples 101 and 104 prepared in Example 1,
Exemplary compound used in the emulsified dispersion (Exemplary compound (P-56) with a molecular weight of 70,000, P-57, with a molecular weight of 95,000
Samples were prepared in which the exemplified compound (P-59) with a molecular weight of 1,000,000 and the exemplified compound (P-65) with a molecular weight of 155,000 were substituted, and samples 111 and 112, and samples 113 and 114, respectively, were prepared.
, samples 115 and 116. These samples and samples 102 and 105 were subjected to the same treatments and tests as in Example 2, and the results shown in Table 6 were obtained. Here, the sensitivity immediately after coating is for sample 111.113.115 and for sample 102.
The sensitivity of sample 112.114.11 is set as 100.
6, the sensitivity of the sample 1°5 is expressed as 100.

Sample 111.113.115 is a sample of the present invention, and sample 102.105.112.114.116 is a sample outside the present invention, but only the sample of the present invention has good sensitivity, storage stability, and color image fastness. At the same time, it turns out to be excellent.

Example 9 Sample 101.102.104 produced in Example 1
．． 105, the exemplified compound used in the emulsified dispersion (C
-1) to exemplified compounds (C-3), (C-12), (C-
Samples were prepared by replacing 37) with equimolar amounts, and samples 117 to 120, samples 121 to 124, and sample 12 were prepared.
The number was increased from 5 to 128. In addition, samples were prepared in which the exemplified compound (M-15) was replaced with the exemplified compounds (M-12) and (M-16) in equimolar amounts, and samples 129 to 132 and 132, respectively, were prepared.
Samples 133 to 136 were used. Furthermore, exemplified compound (Y-1
) was replaced with Exemplified Compound (Y-2) in an equimolar amount to prepare samples 137 to 140. These samples were subjected to the same treatments and tests as in Example 2, and the results shown in Table 7 were obtained.

For each sample, the results for the unchanged photosensitive layer were similar to the results of the previous examples, so only the photosensitive layer for which the change was made is shown.

Here, the sensitivity immediately after coating is 1 for the sample changed from sample 101, and the sensitivity of the sample changed from sample 102.
The sensitivity of the sample changed from sample 105 was expressed as 00, and the sensitivity of the sample changed from sample 105 was expressed as 100 relative to the sample changed from sample 104.

Sample 117.121.125.129.133.137
is a sample of the present invention, and the sample from that pond is a sample outside the present invention.

It can be seen that only the sample of the present invention is excellent in sensitivity, storage stability after coating, and color fastness at the same time.

These samples 117 to 140 were also tested using the treatments shown in Example 2 and Example 3, and the results were almost the same as those for the treatments of Example 1 shown in Table 7.

Similar tests were also carried out on these samples by subjecting them to the treatment shown in Example 4, but the color image fastness results were as shown in Table 4 compared to Table 3, with only one large degree of fading. Again, the results were almost the same as in Table 7.

From the above, it is understood that the sample having the aspect of the present invention exhibits the best performance in all treatments.

Implementation-10 An emulsion for a red-sensitive layer was prepared as follows.

Add 30 g of lime-treated gelatin to 1000 cc of distilled water, dissolve at 40°C, adjust the pH to 6.0 with sulfuric acid, and add 6.5 g of sodium chloride and 0.02 g of N,N'-dimethylethylenethiourea. The temperature was raised to 67.5°C. A solution of 62.5 g of silver nitrate dissolved in 750 cc of distilled water, 26.3 g of potassium bromide, and 8 g of sodium chloride.
．． 6g dissolved in 500oc of distilled water at 67.5℃
The mixture was added to the above solution and mixed for 40 minutes while maintaining the temperature. Furthermore, a solution of 62.5 g of silver nitrate dissolved in 500 oc of distilled water, 17.5 g of potassium bromide, and 12.9 g of sodium chloride were added.
A solution prepared by dissolving the above-mentioned mixture in 300 cc of distilled water was added and mixed for 20 minutes at 62.5°C. When the obtained emulsion was observed under an electron microscope, it was found that cubic grains having an average side length of about 0.46 mm were formed. When the grain size distribution of this emulsion was measured, it was found to be a monodisperse emulsion with a degree of monodispersity of 91%.

After washing this emulsion with desalinated water, 1-
Optimum 1-H sensitization was achieved with ethylnaourea.

This ;'L 11 was designated as J.

Furthermore, by changing the reaction temperature for particle formation, the average side length was reduced to 0.
A similar emulsion with optimal sulfur sensitization was prepared with 33 micron cubic grains and 92% monodispersity. This emulsion was
Emulsions J and I (for 1 odor 0.5 mol 1
Mol Ag and exemplified compounds (III-1), (V-1), (
F-7) and (■-1) were added and used at the end of chemical ripening.

An emulsion for a green-sensitive layer was prepared as follows.

Add 30g of lime-treated gelatin to 1000cc of distilled water, dissolve at 40°C, add 1jJ to 4.2 with sulfuric acid, and add 6.5g of sodium chloride and 0.5g of N,N'-dimethylethylenethiourea. 02g was added and the temperature was raised to 73°C. A solution in which 62.5 g of silver nitrate was dissolved in 750 cc of distilled water, and a solution in which 36.1 g of potassium bromide and 3.8 g of thorium chloride were dissolved in 500 cc of distilled water were added and mixed to the above solution for 40 minutes while maintaining the temperature at 73°C. did. Furthermore, a solution in which 62.5 g of silver nitrate was dissolved in 500 cc of distilled water, and a solution in which 25.2 g of potassium bromide and 9.1 g of arsenic salt 1 were dissolved in 300 cc of distilled water were added and mixed at 67° C. for 20 minutes. did. When the obtained emulsion was observed under an electron microscope, it was found that cubic grains having an average side length of about 0.45 μm were formed. When the grain size distribution of this emulsion was measured, it was found to be a monodisperse emulsion with a degree of monodispersity of 89%. After washing this emulsion with desalted water, it was optimally chemically sensitized with triethylthiourea in the presence of a nucleic acid decomposition product. Call this emulsion L.

Furthermore, by changing the reaction temperature for particle formation, the average side length was reduced to 0.
A similar emulsion with optimal sulfur sensitization was prepared with 33 micron cubes and 93% monodispersity. This emulsion was designated as M.

For emulsion R and M, exemplified compound (III-1), (
v-26>, (v-41), (1-2), and (■-11) were added and used.

Blue! An emulsion for 5 layers was prepared as follows.

Add 30g of lime-treated gelatin to 700cc of distilled water,
After dissolution at 40°C, the pH was adjusted to 5.2 with sulfuric acid, 5 g of sulfur chloride and 0.03 g of N,N''-dimethylethylthiourine were added, and the temperature was raised to 73°C. Ta.

A solution of 31.25 g of silver nitrate dissolved in 750 cc of distilled water, 18°6 g of potassium bromide, and 1.6 g of sodium chloride.
was dissolved in 500 cc of distilled water and was added to and mixed with the above solution for 40 minutes while maintaining the temperature at 73°C. Furthermore, silver nitrate 93
A solution prepared by dissolving 75 g of 75 g of distilled water in 500 cc of distilled water and a solution containing 42.7 g of potassium bromide and 11.3 g of sodium chloride dissolved in 300 cc of distilled water were added and mixed at 69° C. for 20 minutes. When the obtained emulsion was observed under an electron microscope, it was found that cubic grains having an average side length of about 0.82 μm were formed.

This emulsion was a monodisperse emulsion with a degree of monodispersity of 92%.

After washing this emulsion with desalted water, it was optimally chemically sensitized with triethylthiourea in the presence of a nucleic acid decomposition product. This emulsion was designated as N.

Furthermore, by changing the reaction temperature for particle formation, the average side length was approximately 0.
．． A similar emulsion with optimal sulfur sensitization was prepared with 53 micron cubic grains and approximately 90% monodispersity. This emulsion was designated as 0. For emulsions N and O, 1 column shows 1 hi 1 course (1 -
1), (V-36), and (1-2) were added and used at the end of chemical ripening.

A comparative emulsion was prepared as follows.

Add 30g of lime-treated gelatin to 1000cc of distilled water, dissolve at 40°C, adjust the pH to 4.2 with sulfuric acid, add 6°5g of thorium chloride, and raise the temperature to 62.5°C. Ta. A solution in which 62.5 g of silver nitrate was dissolved in 750 cc of distilled water and a solution in which 17.5 g of potassium bromide and 12.9 g of thorium chloride were dissolved in 500 cc of distilled water were mixed into
．． The mixture was added to the above solution and mixed for 40 minutes while maintaining the temperature at 5°C. Furthermore, a solution of 62.5 g of silver nitrate dissolved in 500 cc of distilled water, 17.5 g of potassium bromide, and 12 g of sodium chloride were added.
．． A solution obtained by dissolving 9 g in 300 cc of distilled water was added and mixed over 20 minutes, and 88 cc of a 10% potassium bromide aqueous solution was further added to perform halogen conversion. When the obtained emulsion was observed using an electron microscope, it was found that the equivalent sphere diameter was approximately 0.4.
Slightly collapsed spherical particles with a monodispersity of 84% were formed at 7μ. After washing with demineralized water, the milk was optimally chemically aggravated with triethylenethiourea in the presence of nucleic acid digests. This emulsion was designated as 1].

Emulsion P contains exemplary compounds (III-1), (V-1),
(F-7) and (■-1) were used.

Similarly, silver bromide content 70 mol%, halogen conversion 1
0 mol%, average particle size 0.45μ, monodispersity 85%
A collapsed spherical emulsion was prepared and optimally sulfur-sensitized with triethylthiourea in the presence of nucleic acid digests. This emulsion was designated as Q.

Emulsion Q contains exemplified compounds (III-1) and (■-26).
, (V-41), and (1-2) were used.

Furthermore, in the same manner, an emulsion consisting of spherical grains with a silver bromide content of 70 mol%, a halogen-modified 1fA of 8 mol%, an average equivalent sphere diameter of approximately 0.83μ, and a monodispersity of 83% was prepared, and the emulsion was subjected to the same optimal sulfur sensitization. Emulsion R was obtained by subjecting the emulsion to emulsion R.

Emulsion R contains exemplified compounds (III-1) and (■-36).
, (1-2) were used.

Emulsions A to R contain 2X10' to 8X10 during grain formation.
21rCj16 was added in 'mol/Agmol.

A milk 1hi dispersion for the Red Angus layer was prepared as follows.

An example compound (P-57) with an average molecular weight of approximately 115,000 was added to 5
．． 5g, 5.1g of exemplary compound (C-1), (C-14
), 1 g of exemplified compound (X-9), (X-1
Mix 1.8 g of 0), 2.1 g of (X-12), 2°0 g of exemplified compound (S-25), 464 g of (S-13), and 0.4 g of compound (a) with 15 cc of ethyl acetate. This solution was added to 190 cc of a 10% aqueous gelatin solution mixed with 12 cc of 10% sodium dodecylbenzenesulfonate, and an emulsified dispersion was obtained using a homogenizer. This emulsified dispersion was designated as (nu).

A milk fraction for the green leaf layer was prepared as follows.

Exemplary compound of the present invention with an average molecular weight of approximately 95,000 (P-57
), 13 g of exemplary compound (M-4'), B'l
1.2 g of diagonal gold compound-1), 1.5 g of (B-1)
, 13 g of exemplary compound (S-7''), 6 g of (S-16)
．． 5g of compound (b), 4g of compound (b) and 40Ω of ethyl acetate were mixed and dissolved at 50°C.
The mixture was added to 210 cc of a 10% gelatin aqueous solution mixed with 13 cc of sodium dodecylbenzenesulfonate and dispersed using a homogenizer. This emulsified dispersion (le)
And so.

An emulsified dispersion for the blue-sensitive layer was prepared as follows.

Exemplary compound of the present invention with an average molecular weight of approximately 95,000 (P-57
), 19 g of Exemplified Compound (Y-2), 7.6 g of Exemplified Compound (S-13), and further 4.3 g of Compound (c).
g, and 27 cc of ethyl acetate were mixed and dissolved at 50°C, and this solution was mixed with 18 cc of 10% gelatin aqueous solution mixed with 8 cc of 10% sodium dodecylbenzenesulfonate.
It was added to 0 cc and dispersed using a homogenizer to obtain an emulsified dispersion. This milk item was designated as (wo).

In addition, as an emulsified dispersion for comparison, the above-mentioned emulsified dispersion (
Emulsified dispersions (wa), (chikara), and (yo) were prepared by removing exemplified compound (P-57) from (nu), (ru), and (wo), respectively.

These emulsions J to R and emulsified dispersions (nu) to (yo)
Coating samples 141 to 144 as shown in Table 8 were prepared by combining the above. Samples 142 to 14 in Table 8
Sample No. 4 is Sample 141 shown in Table 9, except that the emulsion or emulsified dispersion is replaced with equimolar amounts of silver or coupler.

These samples all contain exemplified compounds (D-2) and (D
-4) and compound (e) were used.

Table 8 Samples 141 and 142 have the same emulsion mixing ratio.

Samples 141 to 144 were subjected to the same treatments and tests as in Example 2, and the results shown in Table 10 were obtained.

In this example as well, sample 141 of the present invention maintains almost the same sensitivity as comparative sample 142, has improved storage stability after coating, and has both dark fastness and light fastness. has also been greatly improved. Also, comparative sample 143
Ha, color I! Although the A fastness is equivalent to Sample 141 of the present invention, the decrease in emulsion sensitivity is greater than that of Sample 144.
Comparative sample 144, which also shows a large decrease in sensitivity during storage after coating, is inferior to sample 141 of the present invention in terms of storage stability and color image fastness after coating.

It is understood that sample 141 having the structure of the present invention is the most excellent.

Samples 141 to 144, in which the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were alternately replaced, were made for one layer and the same test was conducted. It was the same as each layer shown in Table 1O.

Table 10 Example 11 Samples 141 to 144 prepared in Example 10 were
The test was conducted through the same treatment as in Example 4. Although the color image fastness was slightly inferior to that of Example 10, the results were similar to those in Table 10 for stains.

Implementation PA12 An emulsified dispersion for a green-sensitive layer was prepared as follows.゛10 exemplified compound (P-57) with an average molecular weight of 95,000
g, Log of the exemplary compound (M-1), and the compound shown below (
2 g of g), 1 g of compound (h), 4 g of compound (i)
, 3 g of compound (j), 7.5 g of exemplified compound (S-7)
g, 6 g of Exemplified Compound (S-16) and 2 g of ethyl acetate.
0cc was mixed and dissolved at 50℃, and this solution was diluted to 10%
It was added to 160 cc of a 10% aqueous gelatin solution mixed with 7 cc of a sodium dodecylbenzenesulfonate solution, and emulsified and dispersed using a homogenizer. This emulsified dispersion (
wa).

Exemplary compound (P-57) was removed from the above emulsion (W) to prepare an emulsified dispersion (R).

Similarly, an exemplary compound (P-57
), 10 g of Exemplified Compound (M-2), 2 g of Compound (k) shown later, 3 g of Compound (i), Compound (1)
), 5 g of the exemplary compound (S-7>), 3 g of the exemplary compound (S-7>), and the exemplary compound (
7 g of S-16) and 25 cc of ethyl acetate were mixed and dissolved at 50°C. This solution was added to 160 cc of a 10% demineralized gelatin solution mixed with 7 cc of a 10% sodium dodecylbenzenesulfonate solution, and the solution was dissolved using a homogenizer. The mixture was emulsified and dispersed. This emulsified dispersion was designated as (Y).

An emulsified dispersion prepared by removing the exemplary compound (P-57) from the above emulsion (Y) was designated as (Y).

Samples 141 and 143 prepared in Example PA10 were prepared by replacing the emulsified dispersion of the green sensitive layer with (wa), (chiri), (yo), and (yu). That is, samples 141 and 1
Samples in which the emulsified dispersion of the green-sensitive layer of No. 43 was replaced with (wa) were designated as 145 and 147, respectively, and samples in which (power) was replaced with (power) were designated as 146 and 148, respectively. Similarly, emulsified dispersion (
Let the samples replaced with (y) be 149 and 151, respectively.
The samples replaced with (evening) were 150 and 152, respectively.

These samples 145 to 152 were subjected to the same treatments and tests as in Example 2, and the results shown in Table 11 were obtained. In this example, no changes were made to Red! ! ! Since the same results as in Example 10 were obtained for the first layer and the blue-sensitive layer, only the results for the green-sensitive layer are shown.

Also in this example, samples 145 and 149 of the present invention
It was praised for its shelf life and color image fastness after coating.

(g) CH3CH3 CH3CH3 (i) CH3CH3 (j) Shi? ij CH3 (k) H9C4C4H9 \ / Table 11 (Effects of the Invention) According to the present invention, a silver halide color photographic light-sensitive material having high sensitivity and excellent preservability and color fastness after coating can be obtained.

Claims (9)

[Claims] (1) At least one diffusion-resistant oil-soluble coupler that forms a dye by coupling with an oxidized bed of an aromatic primary amine color developing agent and at least one high-boiling organic solvent are disposed on a support. In a silver halide color photographic material having at least one silver halide photographic emulsion layer containing an emulsified dispersion of lipophilic fine particles, the emulsified dispersion of lipophilic fine particles contains the coupler and a high boiling point organic solvent, Furthermore, it is a dispersion obtained by emulsifying and dispersing a mixed solution in which at least one type of water-insoluble and organic solvent-soluble homopolymer or copolymer consisting of at least one type of repeating unit having no acid group in the main chain or side chain coexists. and the silver halide emulsion is composed of a monodisperse silver chloride, silver chlorobromide, or silver bromide emulsion surrounded mainly by (100) planes and substantially free of silver iodide. Silver chemical color photographic material. (2) A silver halide color photograph according to claim (1), wherein the repeating unit having no acid group of the polymer has a -CO- bond in its main chain or side chain. photosensitive material. (3) A silver halide color photograph according to claim (2), wherein the repeating unit having no acid group of the polymer has a -COO- group in its main chain or side chain. photosensitive material. (4) The repeating unit that does not have an acid group in the polymer has a -CONR_2 group in its side chain (where R represents two substituents that may be the same or different, each of which is a hydrogen atom, a substituted or unsubstituted alkyl The silver halide color photographic light-sensitive material according to claim (2), wherein the silver halide color photographic light-sensitive material has a silver halide color photographic light-sensitive material. (5) The silver halide color photographic photosensitive material according to any one of claims (1) to (4), wherein at least one of the oil-soluble couplers is a phenolic cyan coupler. material. (6) A silver halide color photograph according to any one of claims (1) to (4), characterized in that at least one of the oil-soluble couplers is a pyrazoloazole coupler. photosensitive material. (7) Claims (1) to (6) characterized in that the silver halide emulsion is spectrally sensitized.
The silver halide color photographic material described in any of the preceding paragraphs. (8) The silver halide color photographic material according to claim (7), wherein the spectral sensitizing dye is selected from monomethine, trimethine, and pentamethine cyanine dyes. (9) Claims (1) to (8) characterized in that the silver halide emulsion layer contains at least two kinds of the monodisperse silver halide emulsions. The silver halide color photographic material according to any one of the above.