JPS6177848A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a monodispersed color photographic sensitive material superior in graininess and sharpness and wide in exposure latitude by forming a nonphotosensitive colloidal layer contg. nonphotosensitive fine silver halide grains located near the support side of at least one emulsion layer contg. 2- equiv. yellow coupler, and monodispersed silver halide grains. CONSTITUTION:The 2-equiv. yellow coupler contained in the photographic sensitive material includes a coupler represented by general formula I in which X1 is halogen, alkoxy, or alkyl; Y1 is a group to be released when the coupler couples with the oxidation product of an aromatic primary amine color developing agent to form a dye; R1 is a group substituted at the benzene ring; n is 1 or 2; and R2 is alkyl or aryl.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a novel halogen compound that has a high maximum color density of a color image and has excellent development processing stability. This invention relates to silver oxide color photographic materials.

[Prior art]

In current photographic materials, silver halide grains with substantially polydispersity and a coefficient of variation of particle size distribution of 0.20 or more are often used. With the spread of small-sized films and the accompanying use of small-sized films, significant improvements in sharpness, graininess, etc. are required. It is well known that these problems can be solved by using dispersible silver halide grains. However, the disadvantage of using monodisperse silver halide grains is that the a range r-← is narrower than when polydisperse silver halide grains are used. It is desired to develop a silver halide photographic material that utilizes silver halide grains and has a wide exposure range of − and −+. An object of the present invention is to provide an improved silver halide color photographic material. A second object of the present invention is to provide a silver halide color photographic material with improved sharpness. A third object of the present invention is to provide a monodisperse silver halide color photographic material that has excellent graininess and sharpness and has a wide exposure range of -1.5.

Components of the Invention The object of the present invention is to provide a support with a small number of (both 1j-) emulsion layers containing 2-equivalent yellow kaglar and substantially monodisperse silver halide grains. and an I-silver halide color photographic light-sensitive material, which has a non-photosensitive colloid layer containing substantially non-photosensitive silver halide fine grains on the side closer to the support than the emulsion layer. achieved by.

The yellow coupler used in the present invention has the following general formula C
1).

General formula [I] Y.

Xl: ■Halogen atom, ■Alkoxy group, ■Alkyl group Halogen atom: Chlorine atom, etc. 7A/Coxy group, methoxy group, ethoxy group Ring alkyl group: Methyl group, ethyl group Ring Y: Aromatic primary amine Color development Represents a group that leaves when a dye is formed by coupling with the oxidized form of the main drug (sometimes simply referred to as a leaving component). The following groups are preferred. ■Ali zIYi carbon atom along with nitrogen atom,
Represents a group of atoms required to form a 5- to 6-membered ring with atoms selected from oxygen atoms, crab atoms, and sulfur atoms.

R1: represents a group that can be substituted on the benzene ring, and n is l or 2
represents. When n is 2, R may be the same or different.

Ro is a hydrogen atom, a halogen atom, (e.g. fluorine, chlorine, bromine, etc.) where RC+Rr, RF may be the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent,
Represents an aryl group or a heterocyclic group.

R1: represents an alkyl group or an aryl group. Preferably it is tart-butyl group, phenyl group or 0-methoxyphenyl group.

Next, Y will be explained. The aryl moiety of the aryloxy group represented by Yl is preferably phenyl, but this phenyl may have a substituent.

Specifically, the aryloxy group includes a phenoxy group, 4
-carboxyphenyloxy group, 4-(4-benzyloxybenzenesulfonyl)phenyloxy group, etc.

In addition, examples of the heterocyclic oxy group include l-phenyl-5
-tetrazolyloxy group, inoxasilyloxy group,
Examples include 4-pyridinyloxy group.

Next, typical examples of groups in general formula [I] that can be eliminated during color development are described below.

♂ CH.

Shiri 2L; @j113 (20) O I own) O Next, specific representative examples of the yellow coupler used in the present invention will be shown.

rl Y -25 Y -AY -4Y-Add Y-32CI Hs In the practice of this invention, the 2-equivalent yellow coupler is]
f! Type 1 may be used alone or two or more types may be used in combination. Furthermore, it may be used in combination with 4-equivalent Yellow Kagura.

The addition cap of the 2-equivalent yellow coupler is 2 x 10-5 moles per mole of silver halide, more preferably 1 x 10-1
．． It is 0 mole.

In the present invention, the substantially non-photosensitive I silver halide fine particles contained in the non-photosensitive colloid layer may be those that are substantially non-photosensitive, that is, those that are not substantially developed in the developer. Any silver bromide can be used, but it is preferable that it is not substantially developed or dissolved in the developer, and silver bromide is preferable as the silver iodide composition, and silver iodide content is preferably 2. ~[0 mol% silver iodobromide is more preferred.

In addition, it is preferable that the average particle size is smaller than 0.3μ, and moreover, from the viewpoint of sharpness, the average particle size is less than 0.0μ.
More preferably, it is 2 to 0.2μ. Further, the particle size distribution may be wide or narrow, but a narrow distribution is preferable. The amount of some added is 0.1 to 50 Mg/silver.
ax? s is preferably 1 to 6 .mu./d.

The non-photosensitive colloid layer containing the above-mentioned non-photosensitive fine grain silver halide is said to be close to the emulsion layer containing the 2-equivalent yellow coupler according to the present invention and containing Cαα syn silver grains which are substantially &lL dispersed. This includes not only the case where no pond layer is included between the emulsion layer and the photosensitive colloid layer, but also the case where one or two other non-photosensitive colloid layers are included between these layers, preferably one layer. The following is the case, and it is more preferable that there is no intervening material and the two are in direct contact with each other. The non-photosensitive colloid layer may be, for example, a protective layer, an intermediate layer,
This layer has functions such as a filter layer and an anti-halation layer. Among the above-mentioned layer configurations, 2 according to the present invention
An emulsion layer (hereinafter referred to as the emulsion layer of the present invention) containing an equivalent Yea-a-coupler and substantially monodisperse silver halide grains has one non-photosensitive layer according to the present invention on the side near the support. A layer structure in which the non-photosensitive colloid layer containing a reactive silver halide is in direct contact with the layer is preferred.

From the support side as described below, a red-sensitive silver halide emulsion intermediate layer containing a diffusion-resistant cyan coupler, a green-sensitive silver halide emulsion layer containing a diffusion-resistant magenta coupler, a yellow filter layer, and a wide-fastness layer are formed. In a light-sensitive material formed by successively forming a blue-sensitive silver emulsion layer containing a dispersive yellow coupler and a protective layer, the non-light-sensitive fine-grain silver halide emulsion layer containing a non-light-sensitive silver halide emulsion layer according to the present invention may be used. In order to achieve the effects of the present invention, it is preferable to provide a separate colloid layer (hereinafter referred to as the non-photosensitive colloid layer of the present invention) between the blue-sensitive silver halide emulsion layer and the yellow filter layer.

In the present invention, monodisperse silver halide grains (hereinafter referred to as monodisperse silver halide grains of the present invention) refer to the silver halide weight contained within a grain size range of ±20 inches around an average grain size of 7. is 60ts or more of the total silver halide weight. Here, the average particle size 7 is the particle size rL when the product ni x ri'' of the frequency ni of particles with particle size ri and r- is maximum (3 significant figures, minimum digit numeral: 4 types, 5 people) In the case of spherical silver halide grains, the grain size is defined as the diameter, and in the case of grains with shapes other than spherical, the projected image is converted into a circular image of the same area. The particle diameter can be obtained, for example, by photographing the particle with an electron microscope magnified 10,000 to 50,000 times and measuring the particle diameter or the area of the projected image on the print. (The number of particles to be measured is 1000 indiscriminately.
There must be more than one. ] The above-mentioned expression "consisting of substantially monodisperse silver halide grains" means that silver halide emulsions with different grain sizes can be mixed and used within a range that does not impede the effect of monodispersity. For example, the grain size distribution curve It is meant that the present invention also includes cases where the expression has a plurality of modes.

Including such cases, the grain size distribution of silver halide grains consisting of substantially monodisperse silver halide grains is defined as halogen contained within a grain size range of ±20qk centered on 7 as defined above. The weight of the cured steel particles is 60 es or more, more preferably 70 es or more, particularly preferably 80 es or more.

Further, the monodisperse silver halide grains according to the present invention may optionally contain two or more types of monodisperse silver halide grains having different silver iodide contents as long as they fall within the above definition. Preferred is a halog. In particular, it is desirable that the content of silver iodide in the core and shell is different and that the content in the shell is low. It is preferable that the shell be composed of a shell made of silver halide having a silver oxide content of 0 to 6 mol %, from the viewpoint that the effects of the present invention can be more effectively achieved.

Further, the thickness of the shell is preferably in the range of 0.01-0.1μ.

The distribution state of silver iodide in the above silver halide grains is as follows:
It can be detected by various physical measurement methods, and can also be investigated, for example, by measuring luminescence at low temperatures as described in the Abstracts of the 1986 Annual Conference of the Photographic Society of Japan.

The silver halide grains used in the photosensitive material of the present invention are:
Preferably, the silver halide composition other than silver iodide, including the core/shell type grains, is mainly silver bromide.
The silver chloride content is preferably 10 mol% or less. The shape of the silver halide grains according to the present invention may be, for example, hexahedron, octahedron, tetrahedron, plate, or spherical twin. However, hexahedral, octahedral, and tetradecahedral particles are preferred.

In order to produce the substantially monodisperse silver halogenide grains, it is possible to obtain grains of a desired size by a double jet method while keeping PAg constant. The halogenated anchor agent used in this study was published in Japanese Unexamined Patent Application Publication No. 54-4
The method described in No. 8521 can be applied. For example, it is produced by a method in which a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. At this time, highly monodisperse 7-silver halide grains can be obtained by appropriately selecting the time function of the addition rate, PH, PAg, temperature, etc.

Core/shell type monodisperse silver halide grains can be produced by using monodisperse silver halide grains as a core and covering the core with a shell.

The thickness of the shell that covers the core is such that it does not hide the desirable properties of the core, and such a shell is made by forming monodisperse silver halide grains by a double jet method using a soluble halide compound solution and a soluble silver salt solution. It can be deposited and formed in the core.

The above core/shell type silver halide grains') 'Xl
Regarding the transmission method, for example, West German patent 1,169,29
No. 0, British Patent No. 1.027,146, Japanese Unexamined Patent Publication No. 57-1
It is also described in No. 53232, Japanese Patent Publication No. 51-1417, etc.

In the present invention, for example, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, etc. are allowed to coexist during the manufacturing process of the silver halide grains according to the present invention. It's okay.

The present invention can be used as a single color photosensitive material, but it can also be used as a multicolor photosensitive material. Multicolor color sensitive materials usually have dye image-forming constituent units that are sensitive to each of the three primary color regions of the spectrum, and each constituent unit is a single emulsion layer or a multilayer emulsion that is sensitive to a certain region of the spectrum. (In this case, it is preferable that the respective emulsion layers have different sensitivities) and may have layers such as, for example, a filter layer, an intermediate protective layer, and an undercoat layer. The layers of the sensitive material, including the layers of imaging units, can be applied in various orders as known in the art. Multicolor silver halide emulsions usually have blue sensitivity when kept, but they do not necessarily have to be blue sensitive.

A typical multicolor color sensitive material comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer with at least one diffusion-resistant cyan coupler of the IMM, and at least one diffusion-resistant magenta coupler. a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer with at least one green-sensitive silver halide emulsion layer; a yellow dye imaging unit consisting of at least one!-sensitive silver halide emulsion layer with at least one diffusion-resistant yellow fogger; and a non-photosensitive layer coated on a support.

The diffusion-resistant couplers shown below are preferably used.

As the diffusion-resistant cyan coupler, phenolic compounds and naphthol compounds are preferable, such as those described in U.S. Pat.
, No. 369.929, No. 2,434.272, No. 2,474,293, No. 2.895.

No. 826, No. 3,253,924, No. 3,034
No. 892, No. 3,311.476, No. 3, 3
86.

No. 301, No. 3,419,390, No. 3.458
.

No. 315, No. 3,476.563, No. 3.591
.

383, etc., and methods for synthesizing these compounds are also described in the references.

Furthermore, examples of colored cyan couplers include compounds in which the coupling position of a colorless cyan coupler is substituted with arylazo, and color tone uncouplers in which the dye flows out into the processing bath through reaction with an oxidized product of a color developing agent. can.

Examples of diffusion-resistant magenta couplers include compounds such as pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indasilone. As a pyrazolone magenta coupler, U.S. Patent No. 2.6UO
, No. 788, No. 3゜062.653, No. 3.12
7.269, same number: U.

311.476, 3,419,391, 3
No. 519.429, No. A, 558,318, No. 3684.514, No. 3,888,680, JP-A No. 129538, No. 50-13041, Japanese Patent Application No. 5
No. 0-24690, No. 50-134470, No. 50-
Compounds described in US Pat. No. 156327; as pyrazolotriazole magenta couplers, US Pat.
The compound described in US Pat. No. 2.801,171, No. 2,983
．． 6+) No. 8, No. 3.005.712, No. 3, 6
84,514, British Patent No. 937.621, and JP-A-49-123625 and JP-A-49-31448. Furthermore, U.S. Patent No.: i, 4
Colored magenta couplers (types of colored magenta couplers can also be used) in which the dye is leached into the processing bath by reaction with the oxidized form of the developing agent as described in No. 19+391.

As the diffusion-resistant yellow coupler, the general formula [I] is used.
In addition to the two-component yellow coupler represented by the formula, penzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers, which are generally widely used, can be used.

Examples of these are U.S. Pat.
, 265,506, 3,664,841, 3,408,194, 3,277.155, 3.447,928, 3,415.652 ,
JP 49-13576, JP 48-29432, JP 48-66834, JP 49-10736, JP 4
No. 9-122335, No. 50-28834, No. 50-
132926, etc. together with the synthesis method.

Furthermore, as non-coloring strength jars that can be used in conjunction with the present invention, British Patent No. 861,138, British Patent No. 914,145, British Patent No. 1.109,963, Japanese Patent Publication No. 45-14033, and U.S. Patent No. 3 , No. 580, 722 and Midteilungen Ausden Forscheninglaboratory Ender Agfa Levelkiesen Volume 4 352~
You can choose from those described on page 367 (1964).

Hereinafter, the photosensitive material of the present invention further contains a development inhibitor-releasing compound (
(hereinafter referred to as a DIR compound).

DIR compounds include, for example, U.S. Patent No. 3.148,
No. 062, No. 3,227.554, British Patent No. 2,
No. 010,818, JP-A-52-69624, JP-A No. 55
Compounds that react with oxidized color developing agents to form dyes and release development inhibitors as described in U.S. Pat.
No. 632,345, No. 3,958,993, No. 3
．． No. 938,996, No. 3.928.041, No. 3.961.959, JP-A No. 52-67628, JP-A No. 51-6724, and Japanese Patent Application No. 125202-1982. A compound that releases a development inhibitor but does not form a dye upon reaction with an oxidized form of a color developing agent such as JP-A-54-145135, U.S. Pat. No. 4.248
Compounds that release a development inhibitor through an intramolecular nucleophilic substitution reaction as described in No. 1,962, and compounds that release a development inhibitor through reaction with an oxidized form of a color developing agent;
No. 114946, JP-A-57-154234, compounds that release development inhibitors by electron transfer along conjugated chains upon reaction with oxidized forms of color developing agents, etc. You can choose.

Moreover, this DIR compound may be used alone or in combination of two or more kinds of compounds.

lXl0'' to 1.0 mol.

be.

Various methods can be used to disperse the diffusion-resistant coupler and DIR compound, such as the so-called alkaline aqueous dispersion method, solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate depending on the chemical structure and the like.

In the present invention, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. These dispersion methods are well known, and the latex dispersion method and its effects are described in Japanese Patent Application Laid-open Nos. 49-74538 and 51-59943,
Publications No. 54-32552 and Research Disclosure (Re5earch Dlsclo-nure)
), August 1976, Kuzu 14859, pages 77-79.

Suitable latexes include, for example, styrene, ethyl, +1/acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate.
), 2-(methacryloyloxy)ethyltrimethylammonium methosulfate 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-ingrovir acrylamide, N-(2-(2-methyl-4
-oxopentyl)] homopolymers, copolymers and terpolymers of various monomers such as acrylamide, 2-acrylamido-2-methylpropane sulfo/acid. The oil-in-water emulsion dispersion method is a method of dispersing hydrophobic additives such as couplers, such as U.S. Pat.
．． The method described in No. 322,027 can be applied. That is, after being dissolved in a single or mixed solvent of a high boiling point organic solvent with a boiling point of 1756C or higher such as tricresyl phosphate and dibutyl phthalate and/or a low boiling point organic solvent such as ethyl acetate and butyl propionate, the surfactant is added. After mixing with an aqueous gelatin solution and then emulsifying and dispersing in a high-speed rotary mixer or colloid mill, it can be directly added to a silver halide emulsion, or the emulsified dispersion can be mixed with a low boiling point solvent by a known method, and then this 7. Add to the silver halide emulsion.

In the silver halide color photographic light-sensitive material to which the present invention is applied, the hydrophilic colloids advantageously used to prepare the silver halide emulsion and the hydrophilic colloids used in the non-photosensitive hydrophilic colloid layer include: , derivative gelatin such as gelatin, phenylcarbamylated gelatin, amylated gelatin, phthalated gelatin, colloidal albumin,
Cellulose derivatives such as agar, gum arabic, hydrolyzed cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose,
Acrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing V-tane carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol-vinyl cyanoacetate copolymer, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, protein or Included are polymers obtained by polymerizing a saturated acylated protein and a heptamer having a vinyl group.

The silver halide used in combination with the substantially monodisperse silver halide grains according to the present invention and the silver halide grains used in other emulsion layers include silver bromide and silver chloride. , silver iodobromide, silver chlorobromide, silver chloroiodobromide, and any other materials commonly used in silver halide photographic emulsions are included.

These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these No-Rogge/silveride grains may be normal crystals or twin crystals, and any ratio of the (1, O, O) plane to the [1°1.1] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different insides and outsides. Furthermore, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain.

The silver halide emulsion used in the silver halide color photographic light-sensitive material according to the present invention can be produced by a conventional manufacturing method or a variety of other manufacturing methods, such as the method described in Japanese Patent Publication No. 7772/1983, or the method described in U.S. Pat. ,592,
No. 250, i.e., forming an emulsion of silver salt grains with a solubility greater than or less than that of silver bromide, and then at least part of the grains being It can be prepared by any manufacturing method, such as the so-called convergence emulsion manufacturing method, such as converting it into a salt or silver iodobromide salt, or the Lippmann emulsion manufacturing method, which is made of fine-grained silver halide having an average grain size of 0.1 μ or less. be able to.

The above silver halide emulsion can be sensitized with a chemical sensitizer. Chemical sensitizers are roughly classified into four types: noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers.

Noble metal sensitizers include compounds such as gold compounds, ruthenium, rhodium, palladium, iridium, and platinum. Particularly preferred compounds include chloroauric acid, potassium chlorooleate, potassium aurithiocyanate, potassium chlorooleate, and 2-oxychloride. Examples include rhosulfobenzothiazole methyl chloride, ammonium chlorovaladate, potassium chloroaurate, sodium chloropalatite, and sodium chloroi resort. In addition, when using a gold compound, ammonium thiocyanate and sodium thiocyanate can be used together.

In addition to active gelatin, sulfur sensitizers include sulfur compounds, and particularly preferred compounds include sodium thiosulfate, ammonium thiosulfate, thiourea, thioacetamide, allylisothiourea, and N-7lyl rotanine.

Selenium sensitizers include active and inactive selenized doselenide, selenoacetophenone, selenoacetamide, selenourea, N,N-)methylselenourea, triphenyl 7-osphinselenide, and the like.

Reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethanesulfuric acid/acids, hydrazinium salts, hydrazine derivatives, and the like.

Furthermore, if necessary, the silver halide emulsion may be spectral sensitized by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc. I can do it.

The selection can be arbitrarily determined depending on the purpose and use of the silver halide color photographic light-sensitive material, such as the wavelength range to be sensitized and sensitivity.

The above silver halide emulsion contains 1-phenyl-5-mercaptotetrazole, 3-methylbenzo Thiazole, 4-
Hydroxy-6-methyl-1+ 3 + 3m, 7-
Various compounds such as heterocyclic compounds such as citrazaindene, mercapto compounds, metal salts, etc. can be added.

Hardening of the emulsion is carried out according to conventional methods. The hardeners used are conventional photographic hardeners, such as formaldehyde, glyoxal, aldehyde compounds such as glutaraldehyde, derivative compounds thereof such as their acetals or sodium bisulfite adducts, and methanesulfonic acid esters. compounds, mucochloric acid or mucohalogenic acid compounds, epoxy compounds, aziridine compounds,
Active halogen compounds, maleic imide compounds, active vinyl compounds, carbonimide compounds, isoxazole compounds, N-methylol compounds, isocyanate compounds, or inorganic hardeners such as chrome light pan, zirconium sulfate, etc. I can give it to you.

A surfactant may be added alone or in combination to the above silver halide emulsion. These surfactants include coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, antistatic agents, adhesive resistance agents, and agents for improving photographic properties or controlling physical properties. Materials include natural products such as saponin, nonionic surfactants such as alkylene/oxide type, glycerin type, and glycidol type, higher alkylamines, pyridine, other heterocycles, quaternary nitrogen onium salts, phosphonium or sulfonium. cationic surfactants such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric acid ester groups, anionic surfactants containing acidic groups such as phosphoric ester groups, and amphoteric surfactants such as amino acids and aminosulfonic acids. agent can be used.

The silver halide color photographic light-sensitive material according to the present invention contains pe/citriazoles, triazines, benzophenone compounds or It may also contain an acrylonitrile compound. Especially Ciba Geigy's Chinupi 7P@, 320, 326, 327
, 328 and the like are preferably used alone or in combination.

Furthermore, for the purpose of increasing the stability of color photography, the emulsion layer and/or
Alternatively, a p-substituted phenol can be contained in the non-photosensitive hydrophilic colloid layer which is a layer adjacent thereto. Particularly preferred p-substituted phenols include alkyl-substituted hydroquinones, bishydroquinones, polymeric hydroquinones, p-alkoxyphenols, and phenolic compounds. Furthermore, alkoxy or amyloxy derivatives of 6-chromanol or 6,6'-dihydroxy-2'2'-spirochroman can be used as well.

Silver halide color photographic material according to the present invention, °, ′
Pressures are produced by coating 1.I←+CH total+now on various supports. Examples of this support include films of cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyethylene terephthalate, polyamide, polycarbonate, polystyrene, etc., polyethylene laminate paper, polypropylene synthetic paper, baryta paper, etc. It is selected as appropriate depending on the intended use of the silver halide color photographic light-sensitive material.

These supports are generally subjected to a subbing process to enhance adhesion with the silver halide emulsion layer. Typical undercoat materials used for undercoat processing include copolymers of vinyl chloride or vinylidene chloride, copolymers of vinyl alcohol esters, copolymers containing unsaturated carboxylic acids/acids, butadiene, etc. Copolymers of dienes, copolymers of acetals, copolymers of unsaturated carboxylic acid anhydrides such as maleic anhydride, especially vinyl alcohol esters such as vinyl acetate, copolymers with styrene, or their water , ring-opened products with alkali, alcohols or amines,
Further examples include cellulose derivatives such as nitrocellulose and diacetylcellulose, compounds containing epoxy groups, gelatin or gelatin modified products, and polyolefin copolymers.

Furthermore, gelatin or polyols, monohydric or polyhydric phenols and their derivatives, crosslinking agents (hardeners, metal oxides, etc.) are used in combination with these subbing materials to perform subbing processing. You can also do that.

When actually undercoating a support, the above-mentioned undercoating materials can be used alone or in combination.

Further, these undercoating processes can constitute an undercoat layer by a single layer or a multilayer, but of course, it may be used in combination with an undercoat material and may be further layered. For example, a method in which a layer of gelatin is coated on top of a vinylidene chloride copolymer layer, or a subbing process in which a layer of vinyl chloride + 7 de/copolymer, a mixture of gelatin and vinylidene chloride copolymer, and a gelatin layer are coated in this order. A method of multilayer coating using a combination of materials is carried out, and arbitrary materials can be used in combination depending on the purpose, and multilayer coating can also be performed by using a combination of materials.

In addition to the undercoat processing by the above-mentioned material processing, the surface of the support is subjected to treatments such as corona discharge, glow discharge, other electronic impact flame treatments, ultraviolet irradiation, oxidation treatment, saponification treatment, and surface roughening to form the support and emulsion. It is also possible to glue the layers together. These treatments can be used alone or in combination, but sufficient undercoat processing can also be performed by using them in combination with the above-mentioned material processing.

The silver halide color photographic light-sensitive material according to the present invention includes a color negative film, a color positive film,
It includes all kinds of silver halogenide color photographic light-sensitive materials such as color reversal films and crab 7-heno'-.

The color developing agent used in the development of the silver halide color photographic light-sensitive material of the present invention is an aromatic primary amine compound, and particularly preferably a p-phenylenediamine type developing agent, such as 4-amino-N, N- Diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-ami/-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β -Hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfonamidoethyl-4-amino- N,N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline,
3-acetamido-4-amino-N, N-diethylaniline, 4-amino-N, N-dimethylaniline, N-ethyl-N-β-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl- 4-Aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-
Methyl-4-aminoaniline and salts thereof, such as sulfate, hydrochloride, sulfite, and p-nitoluenesulfonate.

Photographic additives used in these color developing solutions include alkaline agents (for example, alkali metal and ammonium hydroxides, carbonates, and phosphates), pH adjusting agents, and buffering agents (for example, acetic acid, boric acid, etc.). 5 weak acids and bases and their salts), development accelerators (for example, pyridinium compounds, cationic compounds, potassium nitrate, sodium nitrate, polyethylene glycol condensates and their derivatives, nonionic compounds such as polythioethers, polymer compounds containing sulfide esters, other viridis, ethanolamines, organic amines, benzyl alcohol, hydrazines, etc.), antifoggants (such as alkali bromide, alkali iodide, nitrobenciimidazole, etc.), mercaptobenzo Imidazole, 5-methylbenzotrifle, 1-7enyl-5-mercaptotetrazole, compounds for rapid processing liquids, nitrobenzoic acid,
be/zothiazolicum derivatives, 7enazine-N-oxides, stain or sludge inhibitors, interlayer effect promoters,
Preservatives (for example, sulfites, acid sulfites, hydroxylamine hydrochloride, form sulfide, alkanolamine sulfide adducts, etc.)

Silver halide color photographic light-sensitive materials that have been color-developed using such color-developing solutions are processed by conventional photographic processing, such as a stop solution containing an organic acid, a fixing solution containing an organic acid and hypo or ammonium thiosulfate, etc. A stop-fixer containing a fixing agent, a fixer containing a fixing agent such as hypo or ammonium thiosulfate,
Bleach solutions whose main components are ferric salts of aminopolycarboxylic acids and alkali halides, bleach-fix solutions containing ferric salts of aminopolycarboxylic acids and fixing components such as hypo or ammonium thiosulfate, and other stable solutions. It is sufficient to carry out an appropriate combination of treatments selected from treatment with a treatment liquid such as a chemical solution, washing with water, drying, and the like.

Next, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited to these in any way.

[Preparation of polydispersed emulsion]

Silver nitrate aqueous solution and alkali halide aqueous solution were added in advance to gelatin aqueous solution and excess halide, and heated at 60'C.
Then, an aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and an aqueous magnesium sulfate solution were added [precipitation and desalting were performed, gelatin was added, and pAg 7
．． 8, an emulsion with a pH of 6.0 was obtained.

[Preparation of monodispersed emulsion]

While controlling the pAg and PH in the reaction vessel, an ammoniacal silver nitrate aqueous solution and potassium iodide and potassium bromide aqueous solutions were added to a reaction vessel containing silver halide seed particles and gelatin aqueous solution in advance during grain growth. was added in proportion to the increase in surface area. Next, Demol N aqueous solution manufactured by Kao Atlas Co., Ltd. and magnesium sulfate aqueous solution were added to perform precipitation and desalting, gelatin was added, and pAg7.
8, an emulsion with a pH of 6.0 was obtained. In addition, the silver iodide mole % was changed by changing the ratio of potassium iodide and potassium bromide, and the particle size was changed by changing the amounts of ammoniacal silver nitrate and potassium halide.

The core/shell emulsion was produced by the method described in JP-A-54-48521.

Example 1 Samples 1 to 1o were prepared by sequentially coating the following layers on a subbed triacetate paste.

Layer-1...Non-photosensitive fine grain silver iodobromide with an average particle size of 0.03μ as shown in Table-1 was added to an aqueous gelatin solution (natural content 6 mo1%), and as a hardening agent, 1゜2−
Bis(vinylsulfonyl)ethane was processed and non-photosensitive fine grain silver iodobromide was coated at a silver content of 2 my/m and a dry film thickness of 2 μm.

Layer-2...Blue-sensitive silver halide emulsion layer.

Using the following emulsions (■) and (■) as shown in Table-1, 0.25 mol of silver halide and 40.1 ilr of gelatin per 1 emulsion.
Prepared by conventional methods, including 1 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dimethoxy-3,3'-di(3-
sulfopropyl) thiacyanine hydroxytra, then 4-hydroxy-6-methyl-1,3゜3a17-
A blue-sensitive silver halide emulsion was prepared by adding 20.0 rng of mercabutotetrazole in a conventional manner. Furthermore, per 1 mole of silver halide, as shown in Table 1, a yellow coupler was dissolved by heating in a mixture of 50 y of tricundyl 7 male 7 a) and 150 d of ethyl acetate, and dissolved in an aqueous gelatin solution containing sonida triisopropylnaphthalene sulfonate. In addition, a blue-sensitive silver halide emulsion was prepared by adding a dispersion emulsified in a maloid mill, and the dry film thickness was 4.
It was coated so that it was 0μ.

Layer-3...Protective layer Gelatin aqueous solution 100rn containing gelatin 417r and 1,2-bis(vinylsulfonyl)ethane 0.2gr
gelatin at a ratio of 1.3.9 r/Id to a dry film thickness of 1.1.
It was applied to a thickness of 2μ.

Table-1 Emulsion using comparative coupler Emulsion- ■ Monodisperse silver iodobromide emulsion (pumping content 8'T)
o%7:':': 0.49A, logical value! 75%)
Emulsion-〇 Polydisperse silver iodobromide emulsion (natural content 8 molt,
7 M O, 49jl, Rakuyoshi Tsuchichichi) This value is included within the particle size range of ±20qk from the average particle size of 7,
It represents the weight ratio of the copper halide grain weight to the total silver halide grain weight.

(The same applies to the following Examples) After applying white light to each sample obtained in this manner through a '7 Edge, development processing was performed in the following processing steps.

Table 2 shows the yellow coloring results obtained for each sample. Table 2tC shows sensitivity, RMS and
E, 8. The results are shown below.

As a measure of the width of exposure latitude, the linear exposure range (linear exposure range) described in The Theory of the Photographic Process, 4th edition, pp. 501-502 by Chi Eina James,
e5cale, hereinafter referred to as E and S. ) was used.

Sensitivity was expressed as a relative value of the reciprocal of the exposure amount giving a Capri density of +0.1. Granularity is defined as 1 of the standard deviation of density value fluctuations that occur when a dye image with a dye image density of 1.0 is scanned by a microdensitometer with a circular scanning aperture of δμ.
000 times the value.

Regarding sharpness, the sample has spatial frequencies from 3/n to 10
The image was exposed through a wedge varying in the range from 0 to 0, and developed as shown in the examples below.
er Function) was determined, and the MT-F values at spatial frequencies of 10 lines/long and weighted/home were compared to evaluate sharpness.

Processing process (38°C) Processing time Color development 3 minutes 15 seconds Bleach 6 minutes second water wash 3 minutes 15 seconds fixing 6 minutes leap second water wash 3 minutes 15 seconds stability loss 1 minute leap second used in each processing step The composition of the treatment liquid was as follows.

[Color developer composition]

[Bleach solution composition] [Fixer composition] [Stabilizing liquid composition] Development processing was performed under the above conditions.

From Table 2, the following is clear. Sample 1 according to the invention
4 and comparative sample 5, if the coupler according to the present invention is not used, the sensitivity will be lower than the sample according to the present invention, and L
g, s, values also become lower. Invention sample 1 and comparative sample 6
It is easily understood that an increase in L E and S cannot be observed unless a non-photosensitive colloid layer containing fine grain silver halide is provided in the first layer. Furthermore, in a comparison between Sample 1 of the present invention and Comparative Samples 6 and 8, a monodisperse hole array and a coupler according to the present invention were used in the second layer, and a non-photosensitive silver halide containing fine grain silver halide was used in the second layer. It can be seen that by providing one layer, the problem of monodisperse emulsions, which is the narrow exposure range, can be solved without sacrificing the advantages of monodisperse emulsions, such as sensitivity and graininess. .

Example-2 Sample heights 11 to 16 were determined in Table 3 in the same manner as Sample 1 of Example 1.
It was prepared using the emulsion shown in .

Table 3, %14 emulsion (■ emulsion and O emulsion were mixed at a mixing ratio of 8:2.

The above samples were treated in the same manner as in Example 1, and the results shown in Table 3 were excellent. Furthermore, the effects of the present invention can be obtained even when mixed with a polydisperse emulsion, as shown in the sample No. 14.

Example 3 Sample layers 17 to 19 were prepared by sequentially coating the following layers on an undercoated triacetate base.

Sample 417: Layer-1... Red-sensitive emulsion layer Silver iodobromide emulsion containing 6 mol% of silver iodide (average grain size 0.6 μ, silver halide 0.25 mol per 1 kg of emulsion, gelatin Y22)
11 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and anhydrous 9-ethyl-3,3'- was added as a red-sensitive sensitizing dye. G(3-sulfopropyA/)-4,s, 4. '5
'-Shihenzothialupocyanine hydroxy)', anhydrous s, 5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-3, '9-diethyl-3
-(4-sulfophthyl)oxythiacarbocyanine hydroxide, then 4-hydroxy-6-methyl-
0.25.9 of 1,3,3a,7-chitrazaindene was added. Furthermore, 1 kg of this emulsion was added with the following cyan turnip 2-
A red-sensitive silver halide emulsion was prepared by adding 262 ml of the dispersion, and coated to a dry film thickness of 4.0 μm.

(Cyan coupler dispersion) 1-Hydroxy-N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-su7tamide 45.0.9
and 1-hydroxy-4-(:4-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy)-N-(δ-(2,4-di-t-aminophenoxy) butyl]-2-naphthamide disodium salt 4.71 to tricresyl phosphate)25,9
．． Sodium triisopropylnaphthalene sulfonate was dissolved in a mixture of 167 ml of ethyl acetate and 2. It was added to 750 d of a 5% aqueous gelatin solution containing II and emulsified and dispersed in a colloid mill to prepare tooomz.

Layer-2: gelatin/4.0ml per 100rnl of gelatin layer. gelatin aqueous solution containing 0.2 p, 1.2 bissulfonylethane to gelatin 1
．． 3fi/rr? It was applied at a ratio of 1.2 μm to a dry film thickness of 1.2 μm.

Layer-3: Green-sensitive silver halide emulsion layer.

Silver iodobromide emulsion containing 7 mol% silver iodide (average grain size 0.6μ, per 1kl of emulsion) - silver rogenide 0.25
Mol, gelatin 37I! 1'Kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and further anhydrous 5.0 kg was added as a green-sensitive sensitizing dye.
5'-dichloro-9-ethyl-3,32-di(3-sulfopropyl)oxacarbocyanine hydroxide; m
Add water 5,5'-diphenyl-9-ethyl-3,3'-di(3-sulfopropyl)-5,6,5,'6'-sebenzoxacarbocyanine hydroxide, then 4-hydroxy- 6-methyl-1,3,3m, 7-
0.25 g of Chitrazai/Den was added.

Next, 350 at of the following magenta coupler dispersion was added to this emulsion 1 to prepare a green-sensitive silver halide emulsion, which was coated to a dry film thickness of 4.0 .mu.m.

(Magenta coupler dispersion) 1-(2,4,6-trichlorophenyl)-3-[:3
35 g of ゜-(2,4-di-t-amylphenoxyacetamide)penzamide]-5-pyrazolone and 1-(
2,4,6-Trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuph/imidoanilino)-5-pyrazolo/8I as tricresyl phosphate 43.1 Dissolved in a mixture of 143 d of ethyl acetate and 4.0 d of sodium triisopropylnaphthalene sulfonate. @r& Contains 5% gelatin water-soluble!
In addition to 720 d, emulsify and disperse in a colloid mill and add 10
It was adjusted to 00TrLl.

Layer-4...One layer of yellow filter.

Dry film thickness of one layer of yellow filter consisting of yellow colloidal silver: 1
．． It was applied to a thickness of 2μ.

Layer-5...Non-photosensitive colloid layer.

Same as layer-1 of sample A-1 of Example-1.

Layer-6: Blue-sensitive silver halide emulsion layer Same as layer-2 of sample height-1 of Example-1.

Ie-7...protective layer Same as sample/%-1 layer-3 of Example-1.

Sample/1618 Layers-1 to 1fx-3 are the same as sample/1617.

Layer-4...Non-photosensitive colloid layer Same as layer-5 of sample/%17.

Layer-5...Yellow filter layer Same as layer-4 of sample rot 17.

Layer-6...Blue-sensitive silver halogenide layer Same as Sample Demon 17 Layer-6.

Layer-7...Protective layer Same as layer-7 with sample height 17.

Sample 419 Layer-1 to layer-4 are the same as Sample Demon 17.

Layer-5...Blue-sensitive silver halide layer.

Same as layer-6 with sample height 17.

Layer-6...Protective layer Same as layer-7 of sample/1617.

Sample A20 Layers 1 to 4 are the same as sample/1617.

Layer-5, blue-sensitive halogenated stone Same as layer-2 of sample layer 18.

Layer-6 protective layer Sample layer 170 Same as layer 7.

Each sample thus obtained was treated in the same manner as in Example 1. The results obtained for each sample are shown in Tables 3 and 4.

Table 3 Comparison of each sample shows that the fine grain/% silver halide layer according to the present invention is provided as close as possible to the blue-sensitive silver halide layer and as close to the support side as possible, which results in a wider exposure range. It will be easily understood that the effect increases. Also,
When a non-photosensitive colloid layer is provided adjacent to a green-sensitive silver halide emulsion layer, a significant increase in D- of the green-sensitive silver halide layer as shown in Table 3 occurs. Table-4
It can be seen from the figure that the MTF value of the green-sensitive layer of sample /1617 according to the present invention is better than that of sample /1620 in which the blue-sensitive silver halide layer emulsion was changed to a polydisperse emulsion.

Example-4 The non-photosensitive fine-grained silver halide in sample layer 17-5 of Example-3 was changed to non-photosensitive silver iodobromide with an average grain size of 0.35 μm (natural content: 6 mol%). Sample/1620 was prepared in the same manner as sample 417 except for the following changes.

Samples /1617 and A20 were treated simultaneously in the same manner as in Example-1 and the MTF values of the green photosensitive layers were compared. Sample 420 had a smaller MTF value than /1617 and was inferior.

In addition, the view of the fine grains/NQ silver genide in the layer 5 of sample rot 17 is 4W/d m" from 2 #/d m".
The pond changed to t 101'Q / d @' is sample/1
Similarly to 617, each sample 1621 + /1
622 was created. Sample/K 17.1621 *A
When fZ2 was simultaneously treated in the same manner as in Example-1, the blue-sensitive layer paste, E, and S were 2.3 for sample i1617, and
Sample A force.

71622 had an increased LJ,,S, value of 2.5 for both samples, but the MTF value of the green sensitivity of ρ for 1 sample l was inferior to that of the sample layer 17°/l621.

Example-5 sample Similarly to sample layer 17, up to ttC layer-6 were coated.

1-17...1 degree sensitivity High sensitivity silver halide emulsion layer Preparation of silver iodobromide emulsion (average grain size 1.2μ, containing 7 mol% silver iodide) into a polydisperse emulsion This was chemically sensitized using gold and a yellow sensitizer, and then anhydrous 5.57-simethoxy 3°3'-C (3
-sulfopropyl) thiacyanine human mixide,
Then 4-hydroxy-6-methyl-1,3,3a,
7 Tetrazaindene 1.01! and 1-phenyl-
5-Mercaptotetrazole! A back-sensitive and highly sensitive silver halide emulsion was prepared by adding 0.0 da. Furthermore, α-piparoyl-α is used as a yellow coupler per mole of silver halide.
-(l-bendi/I/-2-phenyl-3,5-dioxo-1,2,4-triacyridin-4-yl)-2'-
Chloro-5'-[α-(do,tecyloxycarbonyl)
Add 80 g of pentoxycarbonyl]acetanilide, heat-dissolve a mixture of 40 g of dibutyl phthalate, and 240 d of dithyl acetate, add it to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and emulsify and disperse the dispersion using a colloid mill. In addition, a blue-sensitive, high-sensitivity silver halide emulsion was prepared and coated to a dry film thickness of 2.0 μm.

Layer-8...Protective layer Layer-9...Same as layer 7 of sample 17.

Sample M thus obtained and Sample 17 were treated in the same manner as in Example 1, and when they were compared, it was found that the effects of the present invention can be fully exhibited even when the back sensitive layer has a two-layer structure. Ta. From this fact, it can be predicted that the effects of the present invention will be exhibited even when the blue-sensitive stone has a multilayer structure of three or more layers.

(Effects of the Invention) The silver halide color photographic light-sensitive material of the present invention has a wide latitude and improved graininess and sharpness.

Agent Patent attorney No 1) Parents-in-law 2-cho-in) Arm 4' + lrt 12) 1F December 1985
June 1814 Mr. and Mrs. Commissioner of the Japan Patent Office, Dec. 1 Case Indication 11 (Japanese Patent Application No. 200983 2, Title of Invention Silver Halide Color Photographic Light-sensitive Material Contact Address: 1 Sakura-cho, Kuchino-shi, Tokyo 191 Japan) Konishiroku Photo Unigyo Co., Ltd. (Tel: 0425-83-15
21) Patent Part 5 Supplement 1 Column 1 of Claim 1 of the Subject Specification and Column 6 of Detailed Description of the Invention J Contents of Amendment (1) The claims are amended as shown in the attached sheet. .

Claims: On the support tlr, adjacent to at least one emulsion layer containing a 2-11 yellow coupler and containing substantially monodisperse silver halide grains, close to the support. A silver halide color photographic light-sensitive material, characterized in that a non-photosensitive colloid layer containing substantially non-photosensitive fine silver halide grains is provided on the side thereof.

Claims (1)

[Claims] On the support, on the side near the support, in close proximity to at least one emulsion layer containing a two-equivalent yellow coupler and containing substantially monodisperse silver halide grains, a substantially non-containing layer is provided. A silver halide color photographic light-sensitive material comprising a non-photosensitive colloid layer containing photosensitive fine silver halide particles.