JPS61292636A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a negative type color film remarkably enhanced in sharpness and resolution magnifiable at high rate by forming a green-sensitive silver halide emulsion layer on a support and a photosensitive silver halide emulsion layer and a nonphotosensitive layer containing a nondiffusive dye mainly absorbing green light on the side of an exposure lamp. CONSTITUTION:The silver halide color photographic sensitive material has the green-sensitive silver halide emulsion layer formed on the support and at least one photosensitive silver halide emulsion layer and at least one nonphotosensitive layer containing the nondiffusive dye absorbing green light on the side of the exposure lamp. Said dye is dissolved in high-boiling and low-boiling solvents, mixed with an aqueous solution of gelatin containing a surfactant, emulsifying the mixture with a dispersing means, and added to a nonphotosensitive hydrophilic colloidal solution, and this solution is used.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide color photographic material, and more particularly to a silver halide color photographic material with significantly improved sharpness.

[Prior art]

In recent years, the image quality of silver halide color photographic light-sensitive materials (hereinafter referred to as color light-sensitive materials) has improved considerably, but the sharpness is still not sufficient. In enlarged prints from disk films, etc., roughness (granularity) and poor sharpness of the images significantly reduce the level of print image quality. This is because the sharpness of negative film is not high enough to withstand high-magnification printing. Radiation (light) is reflected at the interface between media with different refractive indexes. In normal photosensitive materials, the interface between the protective layer and air,
This is because reflection occurs at the interface between the silver halide grains and the binder in the silver halide emulsion layer, the interface between the bottom layer and the support, the interface between the back surface of the support and air, etc., seriously impairing the sharpness of the image. Conventionally, various techniques for improving sharpness are known, one of which is a light scattering prevention technique and one of which is an edge effect enhancement technique. The latter technique includes a method using a so-called DIR coupler and a method using a 7-shape mask. Among these, the method using an unsharp mask has a practical limit because it may cause a decrease in sensitivity and deterioration of graininess. D.I.
There are many methods using R couplers (known and useful, as described in Japanese Patent Publication No. 55-34933, @
@Sho 57-93344, U.S. Patent No. 3,227,55
No. 4, No. 3,615,506, No. 3,617゜291
There are compounds described in No. 3,701,783, etc. However, when using a DIR coupler to emphasize the edge effect, the MTF (mod
ulation transfer fancLi
(on=modulation transfer function) is improved, but an improvement in MTF in the high frequency region necessary for high magnification cannot be expected, and undesirable side effects such as a decrease in sensitivity and a decrease in density occur. Diffusive DIR, timing DIR, etc., so-called long distance #l
If a DIR coupler is used, which has an effect up to 300 degrees, the decrease in sensitivity and density can be reduced, but the area of improvement in MTF shifts further to the lower frequency side, and it is not expected to improve sharpness much at high magnifications. On the other hand, as techniques for preventing light scattering, a method of adding a colored substance, a method of forming a thin film, etc. are known. The latter method involves a significant reduction in the amount of silver coated, but it also reduces the number of coloring points, leading to deterioration in graininess. In addition, gelatin, coupler,
There are six ways to reduce the amount of coupler solvent, etc., but all of them have their limitations as they result in a decrease in coating properties and coloring density. In the former case, attempts have been made for a long time to add colored substances to suppress light scattering and improve sharpness, including the following methods. (a) Antihalethane layer This layer is always provided on the side of the emulsion layer away from the exposure source, between the emulsion and the film base, or on the back of the film base. The purpose of this layer is to penetrate the emulsion layer downwards to capture light reflected at optical interfaces such as gelatin-support or support-air, to avoid obscuring by so-called ``reflection halide''. One example of this is to absorb as completely as possible is West German Patent Publication No. 2,711,22.
It's in number 0. Therefore, the ideal color for this layer is black. That is, this layer should exhibit strong and uniform absorption over as much of the visible spectral range as possible. (b) Dyeing of the emulsion layer Filter dyes are added directly to the emulsion to absorb light scattered by the silver halide crystals and to prevent so-called "scattering" from occurring. Staining is commensurate with the sensitivity of each layer, resulting in considerable loss of sensitivity and gradation. (c) Filter Interlayer This layer serves both to improve color reproduction and to improve sharpness. Viewed from the exposure source, this layer is always below the layer whose sharpness is to be improved, so the Haleshi due to reflection in the sense of (a)
It also acts as a protective layer against light scattered back by the silver halide crystals of the underlying emulsion layer, thereby contributing to haleysilane reduction by scattering. At the same time, this layer improves the color reproduction of the underlying emulsion layer, since it prevents unwanted exposure in spectral regions outside the sensitivity range reserved for recording information. The filter interlayer must therefore absorb as much light as possible in this region of interfering secondary sensitivity - the spectral region in which the highest sensitivity lies one filter layer further away from the exposure source. must not absorb any light. An important example is a yellow filter layer of a force 2-sensitive material that corrects the undesirable blue sensitivity of an emulsion layer sensitized for green or red light. The techniques for using dyes as described above have the problem that the effect of improving sharpness is insufficient or the sensitivity decreases so much that a sufficient amount of dye cannot be used to improve sharpness. Also,
At present, it is not possible to improve the MTF value in the above-mentioned high frequency range to a point where it can withstand practical use. Therefore, there is a need for the development of a technique that improves the MTF value in the high frequency range while minimizing sensitivity loss by using dyes appropriately.

[Purpose of the invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color photosensitive material with markedly improved sharpness, particularly a negative color film that can withstand high-magnification enlargement.

[Structure of the invention]

In order to achieve the above object, the present inventors have conducted extensive research into the method of using dyes in multilayer color light-sensitive materials. When a silver emulsion layer and at least one non-photosensitive layer are present, the green light-absorbing dye is localized in the light-sensitive silver halide emulsion layer; The inventors have found that the effect of improving sharpness is significantly greater for the same decrease in sensitivity when localized. That is, the above object is to form a green-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer on a support. It has at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer 1 g closer to the light source than the emulsion layer, and the non-photosensitive layer contains a non-diffusive dye that mainly absorbs green light. The effects of the present invention will be clarified in the examples described below, but it is probably because light is transmitted between the two light-sensitive silver halide emulsion layers, the scattering layer and the scattering layer. Because it is repeatedly reflected, in a layer without a scatterer (non-photosensitive layer), in a plane parallel to the support,
It is considered that the addition of a dye to the non-photosensitive layer effectively suppresses the transmission over a considerable distance and blurring the image. Therefore, in order to make the effect of the present invention effective, it is preferable that the dye is substantially localized in a designated non-photosensitive layer (=non-scattering layer), and the dye is substantially localized in a designated light-sensitive silver halide layer (=non-scattering layer). It is preferable to prevent migration to the scattering layer). This is because when a dye is incorporated into the photosensitive layer, the effect of improving sharpness is small, even though it causes severe desensitization as is clear from the examples. The present invention will be explained in more detail below. A non-diffusive dye that mainly absorbs green light (hereinafter referred to as a non-diffusive green light-absorbing dye of the present invention) is a dye that is added at the time of preparing a non-photosensitive hydrophilic colloid layer in the manufacturing process of a color photosensitive material. Any dye can be used as long as the above-mentioned dye substantially exists in the non-photosensitive hydrophilic colloid layer without diffusing into other layers even after completion of production and has an absorption maximum at 500 to 600 n-. . Further 530-570n
Those having an absorption maximum at m can be preferably used. As an example of a non-diffusible dye, for example, by coexisting a diffusible acid dye and a polymeric mordant containing a basic group in the same non-photosensitive hydrophilic colloid layer, the acid dye is made non-diffusible and used. be able to. The basic mordant used in the present invention is preferably a polymeric mordant containing a basic group, such as imidazole,
Examples include polymers containing pyrinone, furkyl 7-minoalkyl (meth)acrylate, or quaternary salts thereof, and aminoguanidine. These basic mordants preferably used in the present invention are disclosed in U.S. Pat.
, No. 564, No. 2,675°316, No. 2,882.15
No. 8 and No. 3,708,563, and among these, a particularly preferred basic mordant is described in U.S. Pat. No. 2,888.
It is a condensation product of polyvinyl alkyl ketone or poly-N-oxoalkyl(meth)acrylic 7mide and 7mi/guanidine described in Nos. 2,156 and 3,708,563. Next, representative examples of basic mordants preferably used in the present invention are listed. Mordant-1 -(CI2-CI)n -n=500 Mordant-2 Mordant-3 (CH2-ell)n n=300 Mordant-4 -(CO2-C1l)n -n=300C=0 ■ NH In the present invention The dye used is preferably an acidic dye having a sulfo group or a carboxyl group, such as azo, triphenylmethane, anthraquinone, styryl, pennolidene, merocyanine, or oxonol dyes. Next, typical examples of acid dyes used in the present invention are listed. G-1 NH. G-2 G-3 G-4 Preferred non-diffusive green light-absorbing dyes in the present invention include conventionally known high-boiling organic solvents and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, nclohexane, tetrahydrofuran, carbon tetrachloride, After dissolving in a low-boiling organic solvent such as chloroform, it is mixed with an aqueous gelatin solution containing a surfactant, and then mixed with a stirrer, homogenizer,
After being emulsified and dispersed using a dispersing means such as a colloid mill, a 70-knot mixer, or an ultrasonic dispersion device, it is used by adding it to a non-photosensitive hydrophilic colloid solution. Conventionally known high boiling point organic solvents used include R acid 7
amides, carbamates, esters, ketones, urea derivatives, etc., especially diethyl 7-talate, diethyl 7-talate, dipropyl 7-talate, diptyl 7-talate, C-n-cutyl 7-thalet, diisooctyl 7-talate, diamino 7-talate, 7-talic acid esters such as tunonyl 7-talate and diisodecyl phthalate, tricresyl phosphate, triphenyl phosphate, tri(2
- Phosphate esters such as ethylhexyl) phosphate, tricresyl phosphate, sebanate esters such as dioctyl sebacate, cy(2-ethylhexyl) sebacate, and diisodecyl sebacate, and glycerol esters such as glycerol tripropionate and glycerol tributyrate. Esters, others, 7 nobic acid ester, geltaric acid ester, succinic acid ester, maleic acid ester, 7 malic acid ester, citric acid ester,
One or more phenol derivatives such as di-t-7 minophenol and n-octylphenol can be used in combination. Examples of preferred non-diffusive green light absorbing dyes for use in the present invention include the reaction products of known magenta couplers and known color developing agents. Specifically, magenta couplers include pyrazolone,
Examples include pyrazolotriazole couplers, virazolinobenzimiguzole couplers, and ingzolone couplers. As such a magenta coupler, U.S. Patent 2,
No. 600.788, No. 2,983゜608, No. 3,0
No. 62,653, No. 3,127,269, No. 3,31
1゜476, 3,419.391, 3,519
, No. 429, No. 3,558゜319, No. 3,582,
No. 322, No. 3,615,506, No. 3,834゜9
No. 08, No. 3,891.445, West German Patent No. 1,810
, No. 464, West German Patent Application (OLS) 2,408,66
No. 5, No. 2,417,945, No. 2,418,959
No. 2,424,467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 49-74027, Japanese Patent Publication No. 49-74028,
No. 49-129538, No. 50-60233, No. 50
-159338, 51-20826, 51-2
No. 6541, No. 52-42121, No. 52-5892
No. 2, No. 53-55122, patent application No. 55-11094
Examples include those listed in No. 3. Known color developing agents to be reacted with the above couplers include aromatic primary amine compounds, especially p7! The nylennoamine type is LF*L<,N. N-diethyl-p-phenylenediamine hydrochloride, N-ethyl-p-phenylenecyamine [[,N. N-tumethyl-p-phenylenediamine hydrochloride, 2-7
Minnow 5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-7 mino 7-niline sulfate, N-
Ethyl-N-β-hydroxyethylamide/aniline, 4
-amino-N-(2-nodoxyethyl)-N-ethyl-
3-methylaniline-9-)luenesulfone), N,
N-diethyl-3-methyl-4-7mino7niline, N-
Ethyl-N-(β-hydroxyethyl)-3-methyl-
4-7 Minoaniline etc. can be mentioned. Other preferred examples of non-diffusive green light absorbing dyes include known colored cyan couplers. Known colored cyan couplers include, for example, U.S. Patent No. 2,521.908, U.S. Pat.
Examples include compounds described in No. 1, etc. Furthermore, U.S. Patent No. 3,476.563 and Japanese Patent Application Laid-Open No. 1987-10
Colored cyan couplers of the type in which the dye flows out into the processing bath by reaction with the oxidation product of a color developing agent, such as those described in No. 135 and No. 50-123341, can also be used. The most preferred colored cyan couplers are compounds represented by the following general formulas CI) to (If). General formula (13-. General formula CI)-b In the formula, R3 and R2 are each a hydrogen atom, 1 to 1 carbon atom,
30 linear or branched alkyl groups, mono- or bicycloalkyl groups (e.g. cyclohexyl group), terpenyl groups (e.g. nobornyl group), aryl groups (e.g. phenyl group, naphthyl group, etc.), heterocyclic groups (e.g. penzimigzolyl group). The above alkyl groups, aryl groups, and heterocyclic groups representing the nonmetallic atomic group d necessary to form a heterocyclic group such as morpholine, benzothiazolyl group, etc.) or morpholine, pyridine, etc. may be substituted, and the substituent Examples include the following groups. Halogen atoms, nitro groups, hydroxy groups, carboxy groups (if the coupler has at least 12 carbon atoms or an equivalent parasto group in the non-coupling position), amide 7 groups, aryl groups, substituted amine 7 groups (alkylamino, dialkylamino , 7nilino, N-furkyanilino, etc.), carboxylic acid ester groups (carboflukoxy, carbo7lyloxy groups, etc.), amide groups (acetamide, butylamide, ethylsulfonamide, N-methylbenzamide, N-propylbenzamide, 4-t-butyl benzamide, etc.), carbamyl group (carbamyl, N-
octadecylcarbamyl, N,N-)hexylcarbamyl, N-methyl-N-71ylcarbamyl, 3-pentadecyl phenylcarbamyl, etc.), sul7amyl group (coupler has at least 12 carbon atoms in the non-coupling position) (N-propylsul7amyl, N-)lylsul77mil, etc.), alkoxy groups (ethoxy, octadecyloxy, etc.), sulfo groups (where the coupler has at least 12 carbon atoms in the non-coupling position) or a corresponding ballast group), substituted sulfonyl groups (methylsulfonyl, octadecylsulfonyl, ethoxysulfonyl, tesylsulfonyl, 7enylsulfonyl, tolylsulfonyl, 7ethylsulfonyl, etc.), etc. Rsl! -CORs and (/ -COORs'?) (Here, Rs represents an alkyl group having 1 to 20 carbon atoms or a substituted alkyl group.) R4 represents a hydrogen atom or a furkyl group having 1 to 10 carbon atoms. General formula (U)-a General formula (II)-b In the formula, R1 and R2 are the general formulas (1)-a and (1)
It has the same meaning as R1 and R2 described in -b. Further, L represents a fullkyleneoxy group having 1 to 6 carbon atoms,
The plow represents 0 or 1. (DD) represents a diffusible dye residue, such as azo, azomethine,
A preferred (DD) representing a diffusible dye residue having a known dye moiety such as indoaniline, indophenol, anthraquinone, etc. is represented by the formula below. (SO,M)n In the formula, R1 is a hydrocarbon residue, R2 is amino, alkyl,
Indicates acylamine octaureido, alkoxycarbonyl, substituted products thereof, carboxyl group, etc. Examples of other preferred non-diffusible green light absorbing dyes used in the present invention include compounds represented by the following general formula (III). General Formula (I[[) %Formula % where Ba1l represents an organic stabilizing group having a molecular size and configuration that renders the compound non-diffusible during development in an alkaline processing composition. Examples of the above organic stabilizing groups include formulas (I) to (I
ll). In the formula, Z represents a group of nonmetallic atoms suitable for forming a saturated carbon ring (5 to 7 rings) bonded at the 5th and 6th positions to the benzene ring to which the OY group is bonded; represents a hydrogen atom or a group whose bond with an oxygen atom is cleaved at a hydroxyl ion concentration of 10-5 to 2 mol/Q, specifically -COR or -CO
OR (here, R is a C1-C18 furkyl group, phenyl group, or fif which may be substituted with a halogen atom)
m7 represents a nyl group). B represents an organic group that makes the stabilizing group represented by the above formula (I) non-diffusible in the photographic element, and is a long-chain alkyl group, or an aromatic group such as a benzene group or a 7-talene group, or an appropriate divalent group. Typical examples include a kill group or an aromatic group such as a benzene group or a 7-talene group. Here, the above-mentioned IJI furkyl group or aromatic group is unsubstituted.
8-, -C-, -8Q, -, -8o-, -N-. -CR2Rs-1CRz=CRs (wherein, R2 represents a hydrogen atom, an alkyl group or an aryl group, R2 and R5 each represent a hydrogen atom, /) Ifden atom, an alkyl group or a 7-aryl group), - and Consisting of one selected from the group consisting of a substituted or unsubstituted aromatic divalent group, a non-aromatic carbocyclic group, or a non-aromatic heterocyclic group, and consisting of one of these or Alternatively, it is a divalent group formed by arbitrarily combining a plurality of these in a linear chain. (II) where W represents an organic group which renders the stabilizing group of formula (If) non-diffusible in the photographic element, typically an aliphatic group having from 8 to 20 carbon atoms, an aromatic group, In the compounds of the present invention, these groups are bonded to the 5th or 6th position of the indole ring via a nitrogen atom, which includes groups having an alicyclic group or a heterocyclic group. In terms of aspects,
-NHCO- group, -NH8O2- group, -NR,- group (R
, represents a hydrogen atom or an alkyl group). W is bonded to the 5th or 6th position of the indole ring, preferably to the 5th position. Examples of the monovalent organic group represented by R5 in formula (U) include alkyl groups and alkoxy groups, and alkyl groups and alkoxy groups having 1 to 3 carbon atoms are preferred. In formula (If), the low molecular group bonded via a carbon atom represented by R2 is preferably a substituent having 1 to 9 carbon atoms, such as an alkyl group having a carbon atom,
(representing a phenyl group and an alkyl group having 1 to 4 carbon atoms, R4 and IRs may simultaneously form a ring). R2 is more preferably unsubstituted or substituted phenyl with a group selected from the group consisting of a halogen atom, an acetylamide group, a methylsulfonamide group, a nitro group, a carboxy group, a sulfo group, a methanesulfone group, an alkyl group, and an alkoxy group. Examples include groups. In the formula, E is directly attached to the above six aromatic rings or a sulfur group (
It may be branched. ), -O-, -S+, -5o2
-, a phenylene group (which may be substituted with a furkyl group, etc.),
), or a halogen atom, a sulfo group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a nitro group, an ami7 group, an alkyl group, which are bonded via a group formed by arbitrarily adjusting these groups. Tl represents an integer of 1 or 2, which may be the same or different; D represents a group represented by -OR or -NHR2. Here, R7 is a hydrogen atom or a hydroxyl ion concentration of 10-5 to 2
Under conditions of mol/Q, the bond between R5 and 0 is open or -C
It is a group represented by -0-R. Here R3 is a furkyl group, especially an alkyl group having 1 to 18 carbon atoms. X in general formula (III) represents a suitable divalent group,
-3o-, -NRICO-, -NR'SO,-. -CR"Rco, -CRco=CR'- (where R' represents a hydrogen atom, an alkyl group, or an aryl group and %R
2 and R3 each represent a hydrogen atom, 10 denene atoms, an alkyl group or an aryl group, 0 or 1. Col in general formula (III) represents a green light absorbing dye component or a dye precursor component. Such ingredients are well known to those skilled in the art and include azo, azomethine, 7zovirazolone, indoaniline, indoenol, anthraquinone, triarylmethane, alizarin, /aronine, nitro, quinoline, cyanine,
Dyes such as indigoids, 7-thalocyanines, metal complexing dyes, etc., as well as leuco dyes, undergo hypsochromic or bathochromic transitions when applied in different well-known environments such as fluctuations in pH values, reactions with complexing substances, etc. [shifted
) dye precursors such as J dyes and the like. Also,
Col is a coupler component such as phenol, naphthol, indacylon, pyrazolone, U.S. Pat.
．． It may also be a compound described in No. 142. These components may have a solubilizing group if necessary. In certain preferred embodiments of p-sulfonamidophenol, Cot represents a preformed dye component. Examples of Col are represented by formulas (IV) to (Vr). (■) (V) (Vl) In the above formulas (IV) to (Vl), Q is at the 5th or 8th position with respect to G, and is a hydroxy group, -NHCOR2 or -NH8O2R2 (in the formula, R2 is the number of carbon atoms represents an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a pencil group, a phenyl group, or a substituted phenyl group having 6 to 9 carbon atoms). G is a hydroxy group, a salt thereof or the formula -OCR3 or -0C
OR, (wherein R1 is an alkyl group having 1 to 18 carbon atoms,
represents a hydrolyzable acyloxy group (represents a 7enyl group or a substituted phenyl group having 6 to 1B carbon atoms). Z is a cyano group, a trifluoromethyl group, a fluorosulfonyl group, a carboxy group, a carboxylic acid ester of the formula -〇〇〇R, (wherein R represents the above), the 2-position relative to the azo bond, or Nitro group at position 3, fluorine, chlorine or bromine atom, C1-8 furkyl- or substituted alkylsulfonyl group, carbon atom & 6-9 phenyl- or substituted phenylsulfonyl group, carbon Atom WL2~5
A furkylcarbonyl group of the formula -802N'R4Rs (wherein R4 represents hydrogen, an alkyl group having 1 to 8 carbon atoms, or a substituted alkyl group, and R1 represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a substituted alkyl group) Furkyl group, pencil group, phenyl group or substituted phenyl group having 6 to 9 carbon atoms, furkyl group having 2 to 7 carbon atoms or substituted alkylcarbonyl group, 7-enyl group having 7 to 10 carbon atoms or a substituted phenylcarbonyl group, a furkyl- or substituted alkylsulfonyl group having 1 to 6 carbon atoms, a phenyl- or substituted phenylsulfonyl group having 6 to 9 atoms, or R1 and R2 are bonded together. (together with the nitrogen atom, represents a morpholif group or a piperidi7 group)
represents a sulfamoyl group of the formula -〇〇N(R,)2 (in the formula, R1 is the same or different and represents the above), and r represents an integer of 1 or 2. Zl represents a hydrogen atom or Z. R1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, a flukoxy group having 1 to 4 carbon atoms, or a halogen atom. D is a cyano group, a sulfo group, a fluorosulfonyl group, a halogen atom, a -8O3-phenyl group, or a carbon atom number of 6
-9 substituted -8O3-phenyl groups, C1-C8 furkyl- or alkylsulfonyl groups, carbon x C6-9 phenyl- or substituted phenylsulfonyl groups, C1-8 furkyl- or Substituted alkylsulfinyl group, phenyl- or substituted phenylsulfinyl group having 6 to 9 carbon atoms, formula -8O, NR, R
Sulfamoyl group of 5 or formula -〇 〇 N (R4)
2 (wherein R4 and c/R, each represent the same as defined above for Z), but there are no more than one sulfo group in the compound and more than one carboxy There are no bases. Next, specific representative examples of the non-diffusive green light-absorbing dye used in the present invention will be shown, but the compounds used in the present invention are not limited to these. G-1 Q G-2 G-3 Rule G-4 G-5 H G-6 G-7 G-8 DG-9 0■ DG-12 DG-13 DG-14 UL;t12 DG-15 DG- 18 DG -17 03H DG -18 DG -19 DG -20 DG-21 0CH+Js3 DG-23 C-24 H DG-25 CsH++ (t) C-26 0■ DG-27 NHCsL 3 (See) Book The non-diffusive green light-absorbing dye of the invention is effective when contained in a non-light-sensitive layer located closer to the exposure source than the green-sensitive silver halide emulsion layer. It is included in the non-photosensitive layer near the exposure source adjacent to the. Of course, the effect of the present invention is not hindered by including it in a plurality of non-photosensitive layers. Furthermore, in the present invention, it is also a preferred embodiment to use the dye-containing layer according to the present invention together with an antihalation layer and/or filter intermediate layer provided closer to the support than the green-sensitive emulsion layer. The dye-containing non-photosensitive layer is a layer that has virtually no effective sensitivity, and contains unsensitized silver halide grains and silver halide grains that do not contribute to density in the normal exposure range even if sensitized. It also includes waste. The normal exposure range here refers to the exposure range in which the photosensitive material is used most frequently.
In terms of negative color film, this is the exposure range when the camera is set to display sensitivity and is exposed to just the right amount of light. The color photosensitive material of the present invention can preferably have the following configuration. For example, a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer, etc., which are formed by directly overlaying high- and low-sensitivity silver halide emulsion layers with the same color sensitivity as upper and lower layers, respectively, are layered from the support side. A non-photosensitive layer is provided between each of the photosensitive layers having different color sensitivities, and a non-photosensitive layer is provided between each of the commercially sensitive layers and the low-sensitivity layer. As described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is a silver halide emulsion layer with a higher sensitivity than the middle layer. It is composed of three silver halide emulsion layers, such as a silver halide emulsion layer with a low sensitivity, with the layer farthest from the support having the highest photosensitivity, and three silver halide emulsion layers whose photosensitivity gradually decreases toward the support. or as described in Japanese Patent Publication No. 55-34932, a blue-sensitive layer, a highly sensitive green-sensitive layer, a highly sensitive red-sensitive layer, A low-sensitivity green-sensitive layer and a low-sensitivity red-sensitive layer are arranged in this order, and a non-photosensitive layer is appropriately provided between these light-sensitive layers, and a high-sensitivity blue-sensitive layer is arranged from the side farthest from the support. high-sensitivity green-sensitive layer, high-sensitivity red-sensitive layer, low-sensitivity blue-sensitive layer,
A low-sensitivity green photosensitive layer and a low-sensitivity red-sensitive layer are arranged in this order,
In addition, a non-photosensitive hydrophilic colloid layer may be provided between these layers. As shown in the example of the preferred layer structure, it is preferable that the photosensitive layer closest to the exposure source is blue-sensitive; in the case of other photosensitive layers, the sensitivity and color reproducibility of the blue-sensitive layer may deteriorate dramatically. do. When there is a plurality of green-sensitive silver halide emulsion layers, it is preferable that the layer that mainly forms the density range used in normal exposure is positioned as the green-sensitive silver halide emulsion layer of the present invention. In this case, this corresponds to the low-sensitivity layer, and in the case of high, medium, and low sensitivity 3N depletion, this corresponds to the medium-sensitivity layer and/or the low-sensitivity layer. As the non-diffusive green light-absorbing dye of the present invention, the above-mentioned oil-soluble dyes from α are preferred because of their sharp absorption spectrum and stable production. Preferred addition 1 of the non-diffusive green light absorbing dye of the present invention is:
Concentration measured with green light in non-scattering state is 0°01~0.3
0, more preferably 0.03 to 0.15
It is. The silver halide emulsion of the present invention includes any silver halide used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. This ends with using . The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after forming seed particles.The method for forming and growing the 0-seed particles may be the same or different. In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them to a mixing tank while controlling pi (and/or p/Ig). By this method, silver halide grains with a regular crystal shape and a nearly uniform grain size can be obtained.After growth, the halogen composition of the grains may be changed using the converging method.The silver halide emulsion is made of: During production, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of the silver halide grains. In the process of forming and/or growing particles, selected from cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), iron salts (including complex salts), and iron salts (including complex salts). It is possible to add metal ions using at least one of these metal elements to contain these metal elements inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, the metal elements can be added inside the particles and/or on the particle surfaces. Reduction-sensitizing nuclei can be added to the surface. The silver halide emulsion may be freed of unnecessary soluble salts after the growth of silver halide grains has finished, or may be left containing unnecessary soluble salts.
loss (hereinafter abbreviated as RD)) No. 17643, item (2). The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer. The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain. Silver halide grains may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical or plate shapes. In the particles, any ratio of the (ioo) plane to the 1lll1 plane can be used. Further, the particles may have a composite form of these crystal forms, and particles of various crystal forms may be mixed. Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle whose value when divided by the average grain size is 0°20 or less.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. ), which indicates the diameter when the image is converted into a circular image of the same area, may be used alone or in combination, or a polydisperse emulsion and a monodisperse emulsion may be mixed. The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions. Silver halide emulsions can be chemically sensitized by conventional methods6, i.e., sulfur sensitization, selenium sensitization, reduction sensitization,
A noble metal sensitization method using a noble metal compound or other noble metal compounds can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it may be a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. In addition, a supersensitizer that enhances the sensitization m of the sensitizing dye may be included in the emulsion. Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes, hemioxal dyes, and the like are used. Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Silver halide emulsions are used during chemical ripening, at the end of chemical ripening, and/or to prevent capri during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to maintain stable photographic performance. After completion of chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added. It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention can be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. can. The hardening agent can be added to the processing solution in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent, but it is also possible to add the hardening agent to the processing solution. A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, section ♦^. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. The emulsion layer of the light-sensitive material contains a dye-forming coupler that undergoes a coupling reaction with an oxidized form of an aromatic 1a amine developer (for example, a p7z nylene diamine derivative or a 7-minophenol derivative) to form a dye during color development processing. is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above. It is desirable that these dye-forming couplers have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. 4v of silver ions need to be reduced? It may be quantitative or diisomeric, in which only two molecules of silver ions are reduced. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful 7-ragments such as hardeners, capri agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, Dll'?, which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor. Compounds may also be used. The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valence group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle separated by the coupling reaction ( (referred to as timing DIR couplers and timing DIR compounds). Also, depending on the purpose, inhibitors that are dispersible after release and those that are not so dispersible can be used alone or in combination. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler. As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used. Examples of magenta dye-forming couplers include known 5-pyrazolone couplers, virazolobenlimigzole couplers, pyrazolotriazole couplers, and rRI! 4-acylacetonitrile couplers, indacylon couplers, etc. can be used. As the cyan dye-forming coupler, a 7-er/- or 7-tole coupler is generally used. Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be dispersed using various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. It can be appropriately selected depending on the chemical structure and the like. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 1.
Dissolve in a high-boiling pre-organic solvent of 50 ° C. or higher using a low-boiling point and/or water-soluble organic solvent as necessary, and stir with a surfactant in a hydrophilic binder such as an aqueous gelatin solution. It may be emulsified and dispersed using a dispersing means such as a homogenizer, a colloid mill, a 70-knot mixer, or an ultrasonic device, and then added to the desired hydrophilic colloid liquid. A step of removing the low-boiling pre-organic solvent may be included after or simultaneously with the dispersion. Examples of high boiling point solvents include organic compounds such as phenol N conductors, alkyl 7-tar acids, phosphoric esters, dimethyl citrate, benzoic esters, alkyl 7-mides, fatty acid esters, and trimesic esters, which do not react with the oxidized form of the developing agent. A solvent is used. Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and examples of water-soluble organic solvents include 7setone. , methyl inbutyl ketone, β-ethoxyethyl acetate, methoxy glycol acetate, methanol, ethanol, acetonitrile, nooxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, diethylene glycol monophenyl ether,
Examples include fenoquine ethanol and the like. When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color capri-preventing agents, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids. Anionic surfactants are used as dispersion aids when a hydrophobic compound is dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using mechanical or ultrasonic waves.
Nonionic surfactants, cationic surfactants and amphoteric surfactants can be used. The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of a light-sensitive material (between the same color-sensitive layer and between different color-sensitive layers), causing color turbidity or deterioration of sharpness. In addition, a color antifoggant can be used to prevent graininess from becoming noticeable. The color anti-capri agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer. The photosensitive material can contain an image stabilizer that prevents deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J. Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials are used to prevent capri and image deterioration due to ultraviolet rays due to discharge caused by charging of photosensitive materials due to friction, etc. 1. Formation of magenta dye by formalin during storage of photosensitive materials. Formalin scavenger is applied to photosensitive materials to prevent deterioration of couplers, etc.
can be used. When the hydrophilic colloid layer of the photosensitive material contains dyes, ultraviolet absorbers, etc. other than the components of the present invention, they may be mordanted with a mordant such as a cationic polymer. Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. A compound that can be preferably used as a development accelerator is RD17.
The compound is a compound described in Section XXI B-D of No. 643, and the development retardant is a compound described in Section XXI E of No. 17643. A black and white developing agent and V/or its precursor may be used to accelerate development or for other purposes. The emulsion layer of the light-sensitive material contains polyfulkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomol monophosphates, quaternary ammonium compounds, urethane derivatives, and urea for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also include derivatives, imiguzole derivatives, and the like. The photosensitive material may be provided with auxiliary layers other than those according to the present invention, such as a filter layer, a halation prevention layer, an irradiation prevention layer, and the like. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other. A lubricant can be added to the photosensitive material to reduce sliding friction. The process ends with adding an antistatic agent to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used to protect the emulsion layer and/or the emulsion layer on the side on which the emulsion layer is laminated to the support. Preferably used antistatic agents which may be used in the colloidal layer are the compounds described in RD 17643 X1lr. The silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material has various properties such as improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and photographic properties (promoting development, hardening, sensitization, etc.). ) Various surfactants can be used for the purpose of improvement. Supports used in the photosensitive material of the present invention include films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and glass plates. . The hydrophilic colloid layer of the photosensitive material is coated on the surface of the support by corona discharge, ultraviolet irradiation, or flame treatment as necessary. ! 1 for improving the adhesion, antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, frictional properties, and/or other properties of the support surface directly or after applying such as It may be applied through more than one subbing layer. When coating photosensitive materials, thickeners may be used to improve coating properties.For example, thickeners, such as hardeners, have quick reactivity and can be added to the coating solution in advance to prevent deltation before coating. For materials that may cause such problems, it is preferable to mix them using a static mixer or the like immediately before application. - Extrusive coating and curtain coating, in which two or more layers are applied simultaneously, are particularly useful as coating methods, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected. To obtain a dye image using the photosensitive material of the present invention, after exposure,
Color photographic processing is performed, and color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, including a process using a bleaching solution and a fixing solution. Instead of the process using a 1-bath bleach-fix solution, the bleach-fix process can be carried out using a 1-bath bleach-fix solution, or a 1-bath bleach-fix solution that allows color development, bleaching, and fixing to be performed in one bath. It is possible to perform a monobath treatment process using In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator treatment process may be performed in which a color developing agent or its precursor is contained in the material and development is performed with a 7 activator solution, or a 7 activator solution may be used for the monobath treatment. Processing can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.) Color development process - Bleach process Constant fixation process - Color development process - Bleach-fixing process Process/Pre-hardening process - Color development process - One stop Fixing process - Water washing process - Bleaching process - Constant fixation process - Water washing process - Post hardening process / Color development process - Water washing process - Supplementary information Color development process - Stop process - Bleach process Constant fixation process/activator process - Bleach-fix process/Activator process - Bleaching process Constant fixation process/Monobath process Processing temperature is usually 10°C It is selected in the range of ~65℃,
The temperature may exceed 65°C, preferably 25°C to
Processed at 45°C. The color developing solution is generally an alkaline aqueous solution containing a color developing agent.The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenyrecinamine-based derivatives. These color developing agents may be used as salts of organic acids or inorganic acids, such as chloric acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. be able to. These compounds are generally used at a concentration of preferably 0.1 to 30 g, more preferably 1 to 15 g, for color developer 11.
Use at a concentration of g. For example, the amino 71-nol fan developer mentioned above is 0-7
These include minophenol, p-7 minophenol, 5-7 mino-2-hydroxytoluene, 2-7 mino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-tumethylbenzene, and the like. Particularly useful primary aromatic amine-based color developers are N, N
'-Noalkyl fl-71 is a nylene diamine compound, and even if the alkyl group and phenyl group are substituted,
Examples of especially useful compounds which may be unsubstituted include N-N-tumethyl-9-phenylenediamine hydrochloride and N-methyl-p-phenylenenoamine hydrochloride m,N. N-noethyl-G+-phenylenenoami>ma salt, 2-
7 minnow 5-(N-ethyl-N-dodecylamino)toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7mi/aniline sulfate, N-ethyl-N-β- Hydroxyethylaminoaniline, 4-
7 minnow 3-methyl-N,N-diethylaniline, 4-
7mi/-N-(2-nodoxyethyl)-N-ethyl-3
-methylaniline-ρ-toluenesulfonate and the like. Further, the color developing agents mentioned above may be used alone or in combination of two or more kinds.Furthermore, the color developing agents mentioned above may be incorporated into the color photographic material. In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution. The color developing solution may contain an alkaline agent commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citranonic acid, and preservatives such as human mixylamine or sulfites. Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, tunotylformamide, or dimethyl sulfoxide can be appropriately contained. The pH of the color developer is usually 7 or higher, preferably about 9.
~13. In addition, the color developing solution used in the present invention may optionally contain antioxidants such as noethyl hydroxyamine, tetronic acid, tetronimide, 2-7 di/ethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, Pentose or hexose, pyrogallol-1,
3-methyl ether etc. may be contained. In the color developing solution, various chelating agents can be used in combination as metal ion is agents. organic phosphonic acids such as ethylidene-1,1-diphosphonic acid;
7-minobolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenenoaminetitralinic acid; oxycarboxylic acids such as citric acid or gluconic acid; phosphonic acids such as 2-phospho/butane-1,2,4-)licarboxylic acids; /
Examples include carboxylic acids, polyphosphoric acids such as tripolyphosphoric acid and hexatsutaphosphoric acid, and polyhydroxy compounds. As mentioned above, the bleaching process may be carried out simultaneously with the fixing process or separately. As the bleaching agent, metal complex salts of PIi acids are used, such as polycarboxylic acids, aminopolycarboxylic acids, etc. An acid or an organic acid such as oxalic acid or citric acid coordinated with a metal ion such as iron, cobalt, or copper is used. Among the above-mentioned PIi acids, the most preferable fi acids include polycarboxylic acids and 7-minoboricarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, ethylenediaminepentaacetic acid, and ethylenediamine-N-(β-oxyethyl).
-N, N', N'-) diacetic acid, propylenenoamine thitraacetic acid, nitrilotriacetic acid, cyclohexanenoamine thitraacetic acid, im/noffl: acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyl ethernoamine thitraacetic acid Examples include acetic acid, glycol ether diamine tetraacetic acid, ethylenedi7minetetrabrobionic acid, and phenylenenoaminetitraacetic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents are preferably used at a rate of 5 to 450 g/1, more preferably 20 to 2509/1. In addition to the above bleaching agents, the bleaching solution may contain a sulfite salt as a preservative, if necessary. In addition, the bleaching solution is ethylenedi7minetetraacetic acid iron (1
) It may be a liquid containing a complex salt bleach and having a composition in which a large amount of a halide such as ammonium bromide is added.
As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. Bleaching solutions include JP-A No. 46-280 and JP-A No. 45-85.
No. 06, No. 46-556, Belgian Patent No. 0,9
Various bleaching accelerators described in Japanese Patent Publication No. 10, Japanese Patent Publication No. 45-8836, Japanese Patent Publication No. 53-9854, Japanese Patent Application Laid-open No. 71634-1987, and Japanese Patent Publication No. 49-42349 can be added. The pit of the bleaching solution is used at 2.0 or more, but generally it is used at 4.0 to 9.5, preferably 4.5 to 8.0.
It is used in Japan, and the most treacherous score is 5.0 to 7.0. A fixer having a commonly used composition can be used. The fixing agent may be a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate salt such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate. Typical examples thereof include thiocyanates such as potassium ocyanate, sodium thiocyanate, and ammonium thiocyanate, 1,000 urea, and thioether. These fixing agents are used in an amount of 5,971 or more, within a range that can be dissolved, but generally they are used in an amount of 70 to 250,111. Incidentally, a part of the fixing agent can be contained in the bleaching solution, or conversely, a part of the bleaching agent can also be contained in the fixing solution. In addition, the bleaching solution and fixing solution contain boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Various 98 buffers such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants may also be included. In addition, preservatives such as hydroxylamine, hydranone, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, hardening agents such as water-soluble aluminum salts, Organic solvents such as methanol, dimethylsulfonamide, dimethylsulfoxide, etc. can be appropriately contained. The fixer is used at a pH of 3.0 or higher, but generally has a pH of 4.0 or higher.
5 to 10, preferably 5 to 9.5, most preferably 6 to 9. Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the whitening process (above). The preferred compounds and concentrations in the treatment solution are also the same as in the above bleaching treatment step. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylene-7mine iron (III) tetraacetate complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixer mentioned above, or conversely, It is also possible to use a special bleach-fix solution containing a large amount of a halide. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as in the fixing process described above. The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5.

[Example 1] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereby. Example 1 The following layers were sequentially coated on a cellulose triacetate support from the support side to create a multilayer color film sample (1) (the amount added is per 1-2 unless otherwise specified, and Silver halide emulsions are expressed in terms of silver.) 1st layer: Antihalation layer (HC layer) Antihalation layer containing 0.18 g of black colloidal silver and gelatin. 2nd layer: 1st isolation layer (10 layers) 2.5-1-octyl hydroquinone 0.14 g. An isolation layer containing 0.07° of butyl 7-talate (hereinafter abbreviated as DBP) and gelatin. 3rd layer: Low-sensitivity red-sensitive silver halide hole MM (RLN) Silver iodobromide emulsion (emulsion ■) with an average grain size of 0.48 μm and containing 6 mol% silver iodide is spectrally sensitized to red sensitivity. 1.4g,
Cyan coupler (C-1) 0.65g, power 2-docyan coupler (CC-1) 0.06g, tricresylphos 7
A low-speed red-sensitive emulsion layer containing 0.71 g of ET (hereinafter abbreviated as TCP) and gelatin. 4th N: High-sensitivity red-sensitive silver halide emulsion layer (RH layer) average grain size 0.8 gμ theory, silver iodobromide emulsion (emulsion ■) containing 6 mol% silver iodide, spectrally sensitized to red sensitivity. 0.9g, cyan coupler (C-2) 0.9g, T CP 0゜2
Highly sensitive red-sensitive emulsion layer containing 1g and gelatin. Layer 5: Second quarantine! (2G layer) Same as the second layer. 6th M: Low-sensitivity green-sensitive silver halide emulsion layer (GL layer) Emulsion ■ spectrally sensitized to green sensitivity 1.1 g, magenta coupler (M 1 ) 0.48+r, colored magenta coupler (CM -1) 0 .12g%T CP 0.6
A low-speed green-sensitive emulsion layer containing g and gelatin. 7th layer: High-sensitivity green-sensitive silver halide emulsion layer (GHQ) 0.9. , magenta coupler (M-1) 0.19g, colored magenta coupler (CM-1) 0.05g17 CP O, 24g
and a high-sensitivity green-sensitive emulsion layer containing gelatin. No. 81: tJS3@#1lJII (3GJI) Separation layer containing 0.09 g of yellow colloidal silver, 0.14 g of 2,5-di-L-octylhydroquinone, 07 g of D B PO and gelatin. 9th layer: low-speed blue-sensitive silver halide J'1 (BL layer) 0.7 g of low-speed blue-sensitive silver halide emulsion 2 spectrally sensitized to blue sensitivity, YE a-coupler (Y-IN, 17 g, T CPo, 12 g)
and a low-speed blue-sensitive emulsion layer containing gelatin. 10th layer: High sensitivity blue-sensitive silver halide emulsion layer (BH/i
) Emulsion ■ spectrally sensitized to blue sensitivity 0.5g, yellow coupler (Y-1) 0.75g, T CP 00
Highly sensitive blue-sensitive emulsion layer containing 0.8g and gelatin. @11 layer: Protective layer (PL layer) Protective layer containing gelatin! l1M. (C-1) (CC-1> (C-2) OCI(2CQNtlCH2CI(20C1+3(M-
1) Look at C (CM-1) 1ll (y-i) C,! 2 Note that a gelatin hardening agent and a surfactant are added to each layer. Samples (2) to (8) were prepared by adding green light-absorbing dye to sample (1) prepared in this manner as shown in Table 1. In addition, those with oil-soluble dye added (samples 2 to 7)
Next, the same weight of TCP as the dye is added. Each sample was given a wedge exposure using white light and then processed according to the processing steps described below to obtain a dye image. In addition, in order to compare the sharpness, white light was applied through the MTF measurement pattern and the same process was performed to create an MTF curve. The obtained characteristic values are shown in Table 1. The optical density of a dye is the optical density of the dye under green light in a non-scattering state when the same amount of dye is coated with gelatin on a transparent support. This coincides with the increase in the minimum concentration (D m1n). Processing steps (38℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds drying Used in each processing step The composition of the treatment liquid is as follows. (Color development '0.) 4-7 minnow 3-methyl-N-ethyl-N-(β-hydroxyethyl) aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine % sulfate 2.0g anhydrous Potassium carbonate 3F, 5B Sodium bromide
1.38 Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.Of Add water to make IQ. [) White liquid] Ethylenediaminetetraacetic acid iron ammonium salt 100g Ethylenediaminetetraacetic acid diammonium salt 10.0g Amunitum bromide 150.0g Glacial acetic acid
Add 10.0J water and
Q and adjust the pH to 6.0 using aqueous ammonia.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to IQ
and adjust the pH to 6.0 using acetic acid.

[Stabilizer]

Formalin (37% aqueous solution) 1, 5
, Q Konigux (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.
5mQ As is clear from Table 1, the dye is photosensitive ff1 (
Samples localized in GL, BL, and BH (2), (4)
and (5), samples (3), (6), and (7) of the present invention, which were localized in the non-photosensitive layer (3G, PL layer), had a sharpness improvement effect with the same degree of sensitivity reduction. It turns out to be very large. In addition, in sample (8) where dye was added to the non-photosensitive layer (PL layer) but localization was insufficient, a decrease in sensitivity due to dye migration to the photosensitive layer was observed, and desensitization occurred. This shows that the effect of improving sharpness is small despite its large size. Example 2 The following layers were sequentially coated on a cellulose triacetate support from the support side to prepare a multilayer color film sample (9) having a different layer structure from Example 1. First layer: antihalation layer (HCi) first of Example 1
Same as N. Second layer: First isolation layer (same as the second layer of IG Example 1. Third layer: Low sensitivity red-sensitive silver halide emulsion layer (RL layer) Same as the third layer of Example 1. Fourth Layer: $2 isolation layer (2G layer) Same as the 2nd layer of Example 1. 5th layer: Low sensitivity green-sensitive silver halide emulsion layer (GL layer) Same as the 6th layer of Example 1. 6th layer : 3rd interval!N (3G/I) Same as the 2nd layer of Example 1. 7th N: Low sensitivity blue-sensitive silver halide emulsion! (BL layer) Emulsion r of the 9th layer of Example 1. The same as the 9th layer of Example 1 except that emulsion ■ was used. 8th M: 4th isolation layer (4G layer) The same as 2N of Example 1. 9th layer: High sensitivity red-sensitive silver halide emulsion layer (R8 layer) Same as Example 1 except that the emulsion (■) in the fourth layer of Example 1 was replaced with a silver iodobromide emulsion (emulsion ■) having an average grain size of 0.658 rings and containing 6 mol% of silver iodide. !# Same as layer 4. 10th layer: 5th isolation layer (5G layer) Same as 2nd layer of Example 1. 11th layer: High-sensitivity green-sensitive silver halide emulsion layer (GH layer)
The same as the seventh layer of Example 1 except that emulsion (2) in the seventh layer of Example 1 was replaced with emulsion (2). 12th N: 6th isolation/1 (6G layer) Same as the 2nd layer of Example 1. 13th layer: High sensitivity blue-sensitive silver halide emulsion layer (RH layer)
Same as the 10th layer of Example 1. t[: 1st layer (PtN) Same as the 11th layer of Example 1. A gelatin hardener and a surfactant are added to each layer. To the sample (9) prepared in this way, a sample (
10) to (15) were created. Samples (10) to (15)
The same weight of TCP as the dye is added. Samples (9) to (15) were exposed and processed in exactly the same manner as in Example 1, and the results shown in Table 2 were obtained. The display method is the same as in Example 1, except that the MTF value of comparative sample (9) in the ratio MTF column is 24%. Table 2 As is clear from Table 2, the dye was applied to the non-photosensitive layer (3G, 4
Sample (10) of the present invention localized in the G, PL layer), (
12) and (15) are samples (tt)t(t3) and 1/(1
4), MT in the high frequency a range with about the same level of sensitivity reduction.
It can be seen that the effect of improving F is very large.

Claims (2)

[Claims] (1) A silver halide color having a green-sensitive silver halide emulsion layer, at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive layer on the side of the exposure source from the emulsion layer on a support. A silver halide color photographic light-sensitive material, characterized in that at least one of the non-light-sensitive layers contains a non-diffusible dye that absorbs green light. (2) The non-photosensitive layer containing a non-diffusible dye that absorbs green light is located between the green-sensitive silver halide emulsion layer and another light-sensitive silver halide emulsion layer. A silver halide color photographic material according to claim 1.