JPS58130339A - Color photosensitive material - Google Patents

Abstract

PURPOSE:To improve the sensitivity, sharpness, color purity and formalin resistance of a dye image by adding a specified photographic coupler to a green- sensitive silver halide emulsion layer positioned farthest from a transparent support. CONSTITUTION:A transparent support is coated with a red-sensitive silver halide emulsion layer, an intermediate layer, a blue-sensitive silver halide emulsion layer, an intermeditae layer, a green-sensitive silver halide emulsion layer contg. a photographic coupler which reacts with the oxidation product of an aromatic primary amine developing agent, forming a magenta dye image, and a yellow filter layer which doubles as a protective layer. The photographic coupler is represented by formulaI-V (where each of R<1> and R<2> is alkyl, aryl or the like; R<3> is H or a coupling-off group; and Cp is a blocked coupler group forming a colorless or alkali-soluble reaction product after a reaction with an oxidized color developing agent).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide multilayer color photographic light-sensitive material, and more particularly to a silver halide multilayer color photographic light-sensitive material (hereinafter referred to as a multilayer silver halide color photographic light-sensitive material) which is a novel negative-positive printing method with improved sharpness. (referred to as color photographic material).

In recent years, the miniaturization of cameras has been promoted more and more, but the miniaturization of cameras requires a method to make the camera smaller without changing the size of the multilayer color photographic material used or the screen size, and a method to make the camera smaller without changing the size of the multilayer color photographic material used. In some cases, the screen size may be reduced to make the camera smaller. The former method is unrelated to the photographic performance of the multilayer color photographic material because the camera can be made smaller by making the camera parts smaller, but there is a natural limit to the miniaturization of the camera.

On the other hand, the latter is a more effective method that allows the camera to be significantly smaller.

However, as the screen size of a multi-color photosensitive material becomes smaller, the enlargement magnification increases to produce a print of the same size, and the sharpness of the printed image deteriorates accordingly. Therefore, in order to reduce the screen size of multilayer color photographic materials and make cameras more compact, it is necessary to use multilayer color photographic materials with excellent sharpness for high image quality photographic performance. There is a strong need for the development of multilayer color photographic materials that have high-quality photographic performance.

For several important and well-known reasons, subtractive multilayer color photographic materials intended for realistic color reproduction contain at least three separate layers coated on a support such as cellulose ester or polyester. I'm here. Generally, the layer closest to the support contains a silver halide and a cyan coupler that have been spectrally sensitized to the red region of the visible spectrum.

Above this layer is generally a silver halide layer spectrally sensitized to the green region of the visible spectrum and containing a magenta coupler. A third layer above the green sensitive layer is a silver halide layer which is sensitive substantially only to the blue region of the visible spectrum and which contains a yellow coupler.

Conventionally, various methods for improving the sharpness of multilayer color photographic materials have been developed.

Techniques for improving image sharpness are broadly divided into methods that utilize development effects and methods that utilize optical effects.

As a technology that uses optical effects to improve sharpness,
This can be achieved by preventing light scattering caused by halogenated steel particles in a multilayer color photographic material, by preventing halation by using a support, or by devising a layer structure.

For example, JP 51-117032, JP 52-115
There is a method for reducing the amount of silver halide as described in US Pat. A method of reducing the influence of light scattering on the green photosensitive layer while maintaining the effective sensitivity of the blue photosensitive layer, a method of positioning a part of the green photosensitive layer as the uppermost layer described in Japanese Patent Publication No. 53-37018, and an acid dye. Irradiation, such as using a cationic nitrogen-containing activator as a mordant on fine coacervate particles,
Methods for preventing rations are known. However, even with the use of conventionally known methods that utilize development effects and optical effects, it has not yet been possible to obtain the desired performance. In particular, methods that utilize optical effects have disadvantages such as significant desensitization or deterioration of color purity.

On the other hand, in recent years, new building materials that emit harmful gases such as formalin,
As furniture, resin-processed products, adhesives, and the like are frequently used in daily life, there are more opportunities for color photographic materials to come into contact with these harmful gases.

In general, it is desirable that the photographic properties of color photographic materials do not change during long-term use during development, including before and after exposure. However, internal color photographic materials containing couplers are When placed in a gas atmosphere, couplers and other various additives may interact with formaldehyde and change into non-color-forming compounds, or may cause undesirable photographic properties, such as a decrease in color density or gamma. The effects of formalin gas cause serious deterioration of photographic properties such as increasing capri.The effects of formalin gas become even greater as the layer structure of color photosensitive materials changes and miniaturization occurs.The object of the present invention is therefore to A silver halide color photographic light-sensitive material which improves the defects and provides a single dye with excellent sharpness without causing a drop in color purity or desensitization, and in which deterioration of the first dye due to formalin gas is significantly improved. Our goal is to provide the following. Further details will become apparent from the description of the invention that follows.

As a result of intensive research to achieve the above objective, we have developed a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a yellow filter layer, a blue-sensitive steel halide emulsion layer, and a blue-sensitive steel halide emulsion layer on a transparent support. and a protective layer, the uppermost protective layer removing the yellow filter layer and 1. - The following general formula (1) in which the green-sensitive silver halide emulsion layer disposed farthest from the support reacts with the oxidation product of the aromatic primary amine compound to form a magenta dye image. , (I
f) It has been found that a silver halide color photographic light-sensitive material KJ containing substantially the photographic couplers shown in (1), (IV) and (V) can be achieved.

General formula (1) (II) (Otori) (
1 to) (V) In the above formula, R1 and R1 each represent an alkyl group, an aryl group, a heterocyclyl group, an amine group, an acylamino group, a bitroxy group, an alkoxy group, an alkylthio group, or a carboxy group obtained by esterifying a carboxy group. where Ba represents a hydrogen atom or a coupling-off group.

Furthermore, in the above formula, Cp, which is single-bonded to the nitrogen atom forming the heterocycle, becomes colorless after reaction with the oxidized color developing crude drug, producing an alkali-soluble reaction product. Represents a blocked coupler group. The Cp group attached to the coupling position of this preferred magenta dye-forming coupler group is deactivated by -OHR'R'.

Here, R' is alkyl÷0-CO-, alkyl-CO-, aryl-0-CO-, or aryl-CO-.

-C00H, -Notma9 represents 10N, and B
11 is a group defined in R4 above or a group representing aryl-NHCO- (wherein at least one of R' and R1 is substituted with one or more carboxy groups, sulfo groups, or only one hydroxy group) ) The -CHR'R' is detached from the magenta dye-forming coupler group after reaction with the oxidized color developing agent and becomes a mobile alkyl group or an aryl group. It represents a chain group that produces a reaction product.

The present invention will be explained in detail in Section 4 below. The halogenated color photographic light-sensitive material of the present invention is designed to visually improve the sharpness of a dye image in a multilayer color photographic material. A green-light-sensitive silver halide emulsion layer (hereinafter, the silver halide emulsion layer is simply referred to as an emulsion layer) that contributes to the color density is provided at the farthest position from the support, and the edge-light-sensitive emulsion layer is softened according to the general formula described above. As shown in FIG. 1, the green light-sensitive emulsion layer contains a diffusion-resistant coupler which does not adversely affect the sharpness of the dye image and is suitable for improving sensitivity and storage stability. It is characterized by a structure in which a single yellow filter layer is used in combination with the upper capture layer.

First, the magenta couplers each represented by the above general formula contained in the edge-sensitive emulsion layer will be explained in more detail.

The coupling-off group represented by R1 in the general formula according to the invention can be any coupling-off group known in the art. Such groups can modify the properties of the coupler, altering the reactivity of the coupler, or otherwise favorably affecting the coupler coated layer or other layers contained within the element. I can do it. (Based on the fact that after being released from the coupler, it exhibits various functions such as development inhibition, bleaching inhibition, bleaching promotion, color supplementation, etc.).

Representative coupling-off groups include halogen, alkoxy group, aryloxy group, heterocyclyloxy group, sulfonyloxy group, acyloxy group, acyl group, heterocyclyl group, thiacyano group, alkylthio group, arylthio group, heterocyclylthio group, and sulfonamide. groups, phosphonyloxy groups and arylazo groups.

In the present invention, the coupling represented by the above Bj -
Preferred off-groups include groups represented by the following general formulas (Vl) and (■).

General formula (Vl) General formula (Vll),
'-1., In the above formula, X represents an oxygen atom or a sulfur atom, R6 represents an alkyl group, an aryl group, a Peter group, or an acyl group, and Q forms a 5-membered or 6-membered ring. Represents a group of nonmetallic atoms necessary for

Specific examples of preferred coupling-off groups of the present invention represented by the above general formulas (vl) and (■) are described below, but the invention is not limited thereto.

Next, typical couplers according to the present invention are shown below.

(Exemplary couplers) (Coupler 2) (Coupler 3) (ph-phenyl group, R=hydrogen) (Me=methyl group, Bu-butyl group) (Coupler 5) (R-hydrogen or ethyl group) t-pentyl-N h (Coupler 7) (Coupler 8) (Coupler 9) (Coupler 11) (R = hydrogen or ethyl group) (Coupler 12) (R = hydrogen or methyl group) (Coupler 13) (Coupler 14) (Coupler 15) Next As mentioned above, in the present invention, the protective layer provided on the green light-sensitive emulsion layer located at the farthest position from the support is one in which a yellow filter layer is used in combination, The yellow filter density may be 50 or less of the overall yellow filter density of the color photographic light-sensitive material, or may be 100. The red and blue light-sensitive emulsion layers may each contain a coupler other than the photographic coupler represented by the above general formula. Open-chain ketomethylene compounds are used, and generally benzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers are widely used. Two-equivalent type yellow couplers substituted with are also advantageously used. Examples of these yellow couplers include, for example, U.S. Pat.
No. 3,265,506, No. 3,664,84
No. 1, No. 3,408,194, No. 3,447,
No. 928, No. 3.277.155, No. 3,415
, No. 652, Japanese Patent Publication No. 49-13576, Japanese Patent Publication No. 48-1973
No. 29432, No. 48-66834, No. 47-107
No. 36, No. 49-122335, No. 50-28834
No. 50-132926, etc.

In addition, cyan couplers used in the present invention generally include phenol or naphthol derivatives.
Examples of these include U.S. Patent No. 2,423,730;
Same No. 2.474,293, Same No. 2.801171,
No. 2,895,826, No. 3,476,563, No. 3,737,316, No. 3,758,308
No. 3,839,044, JP-A-47-3742
No. 5, No. 50-10135, No. 50-25228,
It is described in No. 50-112038, No. 50-117422, No. 50-130441, etc.

Furthermore, as colored cyan couplers, compounds in which the coupling position of a colorless cyan coupler is substituted with a terzo-substituted compound, such as U.S. Pat. No. 2,521,908, U.S. Pat.
No. 034,892, British Patent No. 1,255,111,
Compounds described in JP-A-48-22028 and the like are generally used. Also, JP-A-50-10135 No. 50-1
23341 and U.S. Pat. No. 3,476,563', a colored cyan coupler of the type in which the dye flows out into the processing bath upon reaction with an oxidized product of the active ingredient is used. 〇 General formulas (1) to (
The magenta couplers according to the invention, respectively designated V), are generally used in amounts of "5 x 10
A range of ' to 8 x 10' moles is preferred. Particularly preferred is 1 x 101 mol to 8 x 10' mol. Depending on the purpose, at least 0 of all couplers used in the silver halide color photographic light-sensitive material according to the present invention may be used.
．． 516 Preferably, a compound which reacts with the oxidized form of the color developing agent to release the present inhibitor, so-called D
Examples of the IR compound include those in which a component that reacts with the oxidized form of a color developing agent directly carries a development-inhibiting component, and those in which a development-inhibiting component is present via a timing group. Here, preferred as the latter DII'L compound is the 〇-general formula [
) A-TIME-Z In the formula, A is a component that reacts with the oxidized form of a color developing agent,
Any active ingredient may be used as long as it can release the TIME-2 group in response to the oxidized form of the color developing agent.

TIMB is a timing group, and Z is a component that suppresses development by being released from a TIME group.A specific example of OTIME is a component that suppresses development by being released from a TIME group. , special request 1977
It may also be due to electron transfer along the conjugated chain as described in the specification of A-17644.
Any compound may be used as long as the -'I'IMB bond is broken to release a TIMR-Z group, and then the TIME-Z bond is broken to release 2.

Disolosure) Volume 176 Nh17643 D
EC, 1978 (hereinafter referred to as Document 1), and preferably include mercaptotetrazole, selnotetrazole, mercaptobenzothiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole, and mercaptobenzimidazole. , selenobenzimidazole,
Includes benzotriazoles, benzodiazoles, and derivatives thereof.

A preferred development inhibiting component is one represented by the following general formula.

General formula (a) R? General formula (b) General formula (c) General formula) ■ 7 General formula (e) General formula (f) In the above formula, R'l is hydrogen, an alkyl group having 1 to 8 carbon atoms. (e.g. methyl, ethyl, butyl), phenyl or substituted phenyl, and Ra is one or more hydrogens and one to four carbon atoms (e.g. chlorine, fluorine, bromine). is a lower alkyl group or nitro group having

More specifically, general formula (8) is the following general formulas (9) and (1
2) or (13).

General formula (9) In the formula, person and 2 have the same meanings as in general formula (8), and the remaining part excluding A and 2 is TIMB of general formula (8).
corresponds to a group, X represents an atomic group necessary to complete a benzene ring or naphthalene ring in which substituents are optional, and R
'l and B111 represent a hydrogen atom, an alkyl group, or an H aryl group.

0 Also, the group -C-Z has an ortho-ma $11 to the O atom.
0 Nine is substituted at the para position 〇 The compound represented by the above general formula (9) is cleaved when it reacts with the oxidized product of the color developing agent, first producing a compound represented by the following general formula (l). , this compound (10) is subsequently cleaved again by electron transfer along the conjugated system to produce a compound represented by the following general formula (11) and simultaneously release 2 [General formula (91) (general formula (10)] [General Formula (11)] The compound represented by the above general formula (11) is a compound called quinone methide or naphthoquinone methide.

General formula (12) % formula % In the formula, M and 2 have the same meanings as in general formula (8), and the 1 -oc- group corresponds to the 71Mm group in general formula (8).
General formula 13) In the formula, M and 2 have the same meanings as in general formula (8), and Nu-X-
E corresponds to TIME in general formula (8). Nu is a nucleophilic group having an electron-rich oxygen, sulfur, or nitrogen atom; oii is a carbonyl, thiocarbonyl, or phosphinyl group with an unpaired electron; and 9 is a nucleophilic group having a thiophosphinyl group. This electrophilic group is an electrophilic group that is ZK-bonded. oX is sterically related to Nu and the capacitor, and after Nu is released from A, a 3- to 7-membered ring is formed. It is a bonding group that can undergo an intramolecular nucleophilic substitution reaction and thereby release 2.

DI with a development inhibiting component via these timing groups
Regarding the R compound, JP-A-54-145135,
It is described in Japanese Patent Application No. 55-17644 S.

On the other hand, a preferred book as a DIR compound in which the component that reacts with the oxidized form of a color developing agent has a direct inhibitory component is 0 represented by the following general formula (14). General formula (14) B- Y In the formula, B is a component that reacts with the oxidized form 1 of the color developing agent, and reacts with the saponified form of the color developing agent to release the Y group (development inhibiting component). ) can be used.

The DIR compound in which the component that reacts with the oxidized form of the color developing agent has a direct inhibitory component is disclosed in U.S. Patent No. 3,958.
, No. 993, No. 3,961,959, No. 3,93
8.996 specification, JP-A-50-147716, JP-A-50-152731, JP-A-51-10-819, JP-A-5
1-6724, JP-A-52-46817, U.S. Pat. No. 3,928,041, U.S. Pat. No. 3,227,554
No. 3,773,201, No. 3,632,34
5, British Patent No. 2.010,818, and Japanese Patent Application Laid-open No. 52-43030.

The aforementioned ゛-general formula s), (12), (13)
A in K and General Formula (14) BK in K includes those that react with the oxidized product of a color developing agent to form a dye and those that do not.

DIR compounds preferably used in the present invention include those represented by the general formula (8) and those represented by the general formula 070, in which the Y group is a benzo) IJ azole group, especially those represented by the general formula ( ) or ().

As the DIR compound used in the present invention, either a DIR compound having a timing group or a DIR compound not having a timing group may be used, or they may be used in combination.

In addition, when an emulsion layer having a certain color sensitivity is composed of a plurality of layers having different sensitivities, it may be contained in two or more of those layers, but it may be contained in at least a low-sensitivity emulsion layer. Preferred O In the color photographic light-sensitive material according to the present invention, when either a DIR compound without a timing group or a DIR compound with a timing group, or both compounds are used in combination, the total amount of the DIR compound is equal to or less than the silver halide in the emulsion. o%Vc is preferably in the range of 5 x 10'' to 5 x 101 mol per 1 mol.0% Vc is preferably in the range of 1 x 10'' to I x 10'' mol, or a mixed mol of both when used together. The ratio can be arbitrarily selected, but the ratio of the DIR compound with a timing group to the DIR compound without a timing group is 0.02.
The color sensitive material of the present invention is a compound represented by the general formula (1) or the fungus according to the present invention. and a DIR compound may be contained in at least one light-sensitive silver halide emulsion layer, for example, in a night-sensitive silver halide emulsion layer, one layer or two or more layers of a green light-sensitive emulsion layer. When the emulsion layer having color properties is composed of layers having different sensitivities, it may be contained in one or more of the layers. The color sensitive material of the present invention is preferably blue-sensitive, It has at least one edge-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer, and contains a non-diffusive coupler combined with each light-sensitive silver halide emulsion layer.

The coupler may be 6-equivalent, 4-equivalent or 2-equivalent to silver ions.

Further, the coupler may be of a low molecular weight, and as a yellow coupler, an open-chain ctomethylene coupler may be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are useful.

These couplers generally contain 2
X 10” mole to 5XIO1 mole, preferably l
X 10" moles to 5 X 10" moles are added.

There are various methods for incorporating the compound represented by the general formula (11 through 11) and the above coupler according to the present invention into a color sensitive material. Latex dispersion method and oil-in-water emulsion dispersion method are particularly effective. These dispersion methods have been known for a long time, and the latex dispersion method and its effects are described in Japanese Patent Application Laid-open No. 49-74538, No. 51-59943, No. 54-32552, and Research Disclosure. (Rese-arch Disclosure
), August 1976, m14850.77-79.

Suitable latexes include, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate),
2-(methacryloyloxy)ethyltrimethylammonium methosulfate), 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-(2-(2-methyl-4)
-oxopentyl)] are homobolymers, hecobolymers, and terpolymers of unique monomers such as acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, and the like. 6. DIR compound used in the present invention, general formula (1) according to the present invention, to which oil-in-water droplet emulsion dispersion method and conventionally known methods for dispersing hydrophobic additives such as couplers can be applied.
The compounds indicated by arrows may be dispersed simultaneously with other couplers, or may be dispersed separately and added independently.

Further, by interposing one or more scavenge layers at appropriate positions in the constituent layers of the color sensitive material, it is possible to control the layer or unit layer affected by the scavenging inhibitor.

As the silver halide emulsion used in the color light-sensitive material of the present invention, any silver halide emulsion used by those skilled in the art can be used.

Any of those used in conventional silver halide emulsions are included, such as silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide or silver chloroiodobromide.

The silver halide grains used in the silver halide emulsion may be coarse or fine, and the grain size distribution may be narrow or wide.It is preferable that the silver halide grains have a narrow distribution. 0 Further, the crystals of these halogenated steel particles may be normal crystals or twin crystals, and any ratio of the (100) plane to the (111) plane can be used. Preferably, normal crystals are used.

According to a preferred embodiment of the present invention, the green-sensitive silver halide emulsion layer disposed at the farthest position from the support is substantially composed of regular silver halide grains, which means that the silver halide grain weight t Or at least 80 grains have a regular shape, and at least 95% of the silver halide grains by weight or number of grains have a regular shape. The term "silver halide grains" refers to grains that do not include anisotropic growth such as twin planes, but grow in an equally favorable or unfavorable manner, and have, for example, cubic, tetradecahedral, octahedral, or spherical shapes. Methods for producing such regular silver halide grains are known, for example, J, Ph0t, 8ci, etc.

332 (1961), Bar, Bunaenges.
, Phys, Chem.

67. 949 (1963), Int@rn, Cong
ressPhoto, 8ci, Tokyo (1967)
It is described in etc.

Furthermore, the crystal structure of these silver halogenide grains may be a uniform layered structure from the inside to the outside, and the inside and outside may have a different layered structure. Silver halide 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. These silver oxide/hardened steel grains can be prepared by known methods commonly used in the art.Although it is preferable to remove soluble salts from the silver oxide emulsion used in the present invention, As a binder for the silver halide emulsion layer of the multilayer color photographic material of the present invention, it is also possible to use a mixture of two or more silver halide emulsions prepared separately. For example, gelatin derivatives such as gelatin, phenylcarbamylated gelatin, acylated gelatin, phthalated gelatin, etc. can be used. These binders may be used in combination with two or more compatible binders as necessary. Can be used as a mixture.

A silver halide photographic emulsion in which the above-mentioned silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in combination in the present invention are roughly classified into four types: noble metal sensitizers.

As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used.

In addition, when using a gold compound, ammonium thiocyanate and sodium thiocyanate can also be used together.

As the sulfur sensitizer, a sulfur compound can be used in addition to active gelatin. As the selenium sensitizer, active and inactive selenium compounds can be used.

Examples of reduction sensitizers include monovalent tin salts, polyamines, bisphosphorylaminosulfide, sila/compounds, isinoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives.The multilayer color photographic material of the present invention includes In addition to the above-mentioned additives, stabilizers, film accelerators, hardeners, surfactants, antifouling agents, lubricants, ultraviolet absorbers, and other various additives useful for photographic materials may also be used in the present invention. The silver halide multilayer color photographic material has 11 layers in addition to the silver halide emulsion layer! , a filter layer, an antihalation layer, a backing layer, and other auxiliary layers may be provided as appropriate.

As the support, conventionally known supports such as plastic film, plastic laminated paper, baryta paper, synthetic paper, etc. may be selected as appropriate depending on the intended use of the photographic material.

Alternatively, the structure described in Japanese Patent Publication No. 56-500272 may be used, in which the upper support has a plurality of aligned black cavities, each of which is open, on one of its surfaces. These supports are generally subjected to a subbing process to enhance adhesion with the photographic emulsion layer.

After exposure of the multilayer color photographic material of the present invention, an image can be obtained by a commonly used color development method.

The basic processing steps in the negative-positive method include color development, bleaching, and fixing steps. Each of these basic processing steps may be carried out using an independent button, but instead of carrying out two or more processing steps, it is also possible to carry out a single processing using a processing liquid that has these functions. For example, a one-bath color processing method containing a color developing agent, a ferric salt bleaching component, and a thiosulfate fixing component, or a one-bath color processing method containing an ethylenecyaminetetraacetate iron(I) complex salt bleaching component and a thiosulfate fixing component. These include bleach-fixing methods.

There is no particular restriction on the processing method for the multilayer color photographic material of the present invention, and any processing method can be applied.For example,
Typical methods include a method in which after color development, bleaching and constant fixing treatment is performed, followed by washing with water and stabilization treatment if necessary; after color development, bleaching and fixing are performed separately, and further washing with water is performed as necessary. A method of performing stabilizing treatment; or a method of performing in the order of prehardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, post hardening, water washing, color development, water washing, supplementary color development, stop, A method in which bleaching, fixing, washing with water, and stabilization are performed in the order of color development, a method in which the developed G1 chain produced by gIK is subjected to no-logenation bleaching, and then color development is performed again to increase the amount of produced dye, a method in which peroxide or Processing may be performed using any method, such as a method of processing a low-graining light-sensitive material using an amplifying agent such as a cobalt complex salt. Examples include P-aminophenol-based ones, and P-phenylenediamine-based ones are representative.

Further, a color developing agent can be added to the multilayer color photographic material for use.

As the precursor of the color developing agent used in the present invention, U.S. Pat.
No. 4, No. 3,342,599 and Research Disclosure Volume 151, Nh15159 Nov, 19
Schiff base type of color active agent described in 1979, Research Disclosure Vol. 129, Nn129240
at, 1976, Volume 121'Yo 12146 Ju
n.

1974, Volume 139, Nn 13924, No.
v, 1975 etc. can be applied.

Moreover, various additives can be added to the color developing solution as necessary.

The sharpness of the dye image obtained in the multilayer color photographic composition according to the present invention, especially the sensitivity, color purity, formalin resistance and sharpness of the dye image obtained in the edge-sensitive emulsion layer located furthest from the support. In other words, the sharpness of the dye image formed on the green-sensitive silver halide emulsion layer of the multilayer color photographic material greatly improves the quality of the printed photosensitive material, which is the final photographic product. This is because it depends on

Furthermore, although the silver halide color photographic light-sensitive material according to the present invention has lower sensitivity than the blue-sensitive silver halide emulsion layer in conventional color light-sensitive materials, the substantial decrease in sensitivity of the color light-sensitive material Light-sensitive silver halide emulsion layer and red-sensitive? - There are almost no problems by adjusting the sensitivity with the logenated emulsion layer.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Comparative Sample 1 Each layer was sequentially applied on a triacetate base coated with an antihalation layer according to the following procedure.

1st layer (red-sensitive silver halide emulsion layer) A high-sensitivity iodobromide emulsion that has been given photosensitivity in the red region by a sensitizing dye (silver iodide content of more than 4 moles, emulsion 100100N, 20g of halogenated Add cyan coupler dispersion (C-1 described below) to 1000 g (containing silver and 3 g of gelatin) in an amount of 8 moles per mole of scissors, and further add the following stabilizers (A) and ( The emulsion solution prepared by adding route 1) has a dry film thickness of 4
．． One cloth was made to have a thickness of 4μ.

('IIJ Stabilizer (B) 2nd layer (intermediate layer) The intermediate layer containing gelatin 0.59/It and 2,5-di-t-octylhydroquinone 0.19/rrt has a dry film thickness of 0.6μ. I applied it to make it look like this.

3rd layer (green-sensitive silver halide emulsion layer) Highly sensitive silver iodobromide (silver iodide content: 4 molt, emulsion 100, 20 g per g) 10009 (containing silver halide and 3 g of gelatin), a magenta coupler dispersion (M-1 described below) was added at a concentration of 8 mol per 1 mol of silver, and the above stabilizers (A) and (B) were added. The emulsion solution prepared by adding
It was applied so that it was μ.

4th layer (yellow filter single layer) 2,5-di-t-octylhydroquinone dispersed with yellow colloidal silver 0.07 g/Trt and gelatin 0
．． One layer of yellow filter containing 99/rrt with yellow density of 1.0. The coating was applied so that the dry film thickness was 0.86 μm.

The fifth layer (blue-sensitive silver halide emulsion layer) contains a yellow coupler dispersion (Y
-1) and then the above stabilizers ((conversion) and (B)).
The dry film thickness of the emulsion solution prepared by adding 7. It was applied so that θμ.

6th Layer (Protective Layer) A protective layer containing 1.39 fi gelatin and 1,2-bisvinylsulfonylethane was coated to a dry film thickness of 0.6 μm.

Comparative Sample 2 Support KJi similar to Comparative Sample 1.Next, the following emulsion solution was prepared and coated, and 90th 1m (red-sensitive silver halide emulsion layer) was prepared in the same manner as the first layer of Comparative Sample 1. Liquid, applied θ2nd layer (intermediate layer) 03rd layer prepared and applied in the same manner as the second layer of comparative sample 1 (
Blue-sensitive silver halide emulsion layer) Same as the fifth layer of Sample 1, except that the sensitivity was made even higher (eight times the sensitivity) than the back-light-sensitive emulsion layer used for the fifth layer of Comparative Sample 1. Solution prepared and applied ρ Fourth layer (intermediate layer) The solution was prepared and applied in the same manner as the second layer of Comparative Sample 1.

5th layer (green-sensitive silver halide emulsion layer) Same as the 3rd layer of sample 1 except that the sensitivity U was slightly lower (9AO times the sensitivity) than the green-sensitive emulsion used for the 3rd layer of comparison sample 1. Similarly [1i liquid,
Applied 0 6th. 1,2-bisvinylsulfonylethane was further added to the adjustment solution used for the fourth layer of Comparative Sample 1 (one layer of yellow filter that also served as a protective layer), and the mixture was coated to a dry film thickness of 0.86 μm. n Comparative Sample 3 The following emulsion solutions were prepared and coated on the same support as Comparative Sample 1 in sequence.

Each floor of the 1st layer, 2nd layer, 3rd layer, 4th layer, and 5th layer was coated with the same solution as sample 2. 6th layer (single layer of yellow filter that also serves as a protective layer) 6th layer of sample 2 The amount of colloidal silver was adjusted so that the yellow filter concentration of one layer of the yellow filter used in The following emulsions were successively prepared and coated on top.

The first, second, third, and fourth layers were prepared and coated in the same manner as Sample 2 above.

Fifth layer (green-sensitive silver halide emulsion layer) The solution was prepared in the same manner as the fifth layer of Sample 1, except that the magenta coupler dispersion (M-1 described later) was changed to (M-2 described later). Coated.

6th layer (one layer of yellow filter serving as protective layer) was prepared and coated in the same manner as the 6th layer of comparative sample 2.

Sample 5 of the present invention The following emulsions were sequentially prepared and coated on the same support as Comparative Sample 1.
The magenta coupler dispersion liquid prepared and applied in the same manner as Sample 2 (○ 5th layer (green-sensitive silver halide emulsion layer)) was mixed (M-2 described later) from (M-3 described later).
The solution was prepared and coated in the same manner as the 5th layer of Sample 4, except that the 6th layer (yellow filter single layer) was prepared and coated in the same manner as the 86th layer of Sample 4.Sample 6 of the present invention Sample 6 Sample 5 except that the magenta coupler dispersion liquid in the fifth layer of Sample 5 was changed from (M-3 described later) to (M-4 described later).
Sample 7 of the present invention The magenta coupler dispersion in the fifth layer of sample 5 was changed from (M-3 described later) to (M-5 described later), and Sample 8 of the present invention The following emulsions were prepared and coated in the same manner as each layer of Sample 5 on the same support as Sample 1.
Coated.

The first layer (blue-sensitive silver halide emulsion layer) was prepared and coated in the same manner as the third layer of Sample 2.

Second layer (intermediate layer) Same as the second layer of sample 2, the third layer (
Red photosensitive halogenated steel emulsion layer) Fourth layer (intermediate layer) prepared and coated in the same manner as the first layer of Sample 2. Same as the fourth layer of Sample 2 except that magenta dye was added. The fifth layer (green-sensitive silver halide emulsion layer) was prepared and coated in the same manner as the fifth layer of sample 6. 0 minute rug prepared and applied in the same manner as the 6th layer (c-1) Non-diffusing cyan coupler (coupler below, CC-1) 5
0, colored cyan coupler (the following coupler, cc-1
) 4g and DIR compound (coupler below, D-1)
0.79 is tricresyl phosphate (TCp)
) and 110 m of ethyl acetate (hereinafter abbreviated as MA), and added to 400 m of a 7.5 tizelatin aqueous solution containing 4 g of sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed in a colloid mill. It was made at 1000m/Kll.

Dispersion (,,y-1) Non-diffusible yellow coupler (coupler below, Y-1) 3
00g and DIR compound (coupler below, T-1) 3
．． 0g is dibutyl phthalate (hereinafter abbreviated as DBp)15
7,5 containing 18g of sodium triisopropylnaphthalene sulfonate heated and dissolved in 0gEIA500m/.
Added to 1600 yt of Chigelatin and emulsified and dispersed in a colloid mill to prepare 2500 ml.0 Dispersion (M-1) Non-diffusible magenta coupler (below coupler, M-1) 4
5g, non-diffusible magenta coupler (below coupler, M-
2) 18g, colored magenta coupler (below coupler, CM-1) 14g and DIR compound (below coupler, D-1) 0.4g, DIR compound (below coupler, T
-1) 0.2g TCP 77F! , BA280m/
The mixture was dissolved in a mixture of
0100O was prepared.

Dispersion (M-2) Non-diffusible magenta coupler (below coupler, M-1) 5
0g, the same magenta coupler (the following coupler, M-2) 2
2.9 and DIR compound (below coupler, D-1) 0
．． 4g, DIR compound (the following coupler, 〒-1) 0.2
Dissolve 8 g of sodium triisopropylnaphthalene sulfonate in a mixture of 280 fF!
was added to a 7,5 qA gelatin aqueous solution soomt containing
Dispersion (M-3) prepared in 65 g of non-diffusible magenta coupler (example coupler 13)
and DIR compound (coupler below, ・D-1) 0, 1
1 f, %DIR coupler (coupler below, T-1) 0
．． After dissolving 1 g of TCp in a mixture of 65 g of TCp and 260 m of ia, the mixture was emulsified and dispersed in the same manner as the dispersion (M-2).

Dispersion (M-4) After dissolving 839 of a non-diffusible magenta coupler (example coupler 8) and 0.19 of a DIR compound (coupler, T-1 below) in a mixture of TCTl 839 and HA 330 m/, the dispersion ( It was emulsified and dispersed and adjusted in the same manner as M-3).

Dispersion (M-s) 88 g of non-diffusible magenta coupler (example coupler 15)
and DIR compound (coupler below, T-1) 0, 15
11 was dissolved in a mixture of 350 ml of 'rcp 889, y, and then emulsified and dispersed in the same manner as the dispersion (M-a),
It was adjusted.

Coupler, c-1 1-hydroxy-4-(β-methoxyethylaminocarbonylmethoxy)-N-(δ-(2,4-sheet t@rt
-amylphenoxy)butyl]-2-naphthamide coupler, CC-1 1-hydroxy-4-(4-(1÷hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy)-N-( δ-(2,4-di-t-amylphenoxyc)butyl]-2-naphthamide disodium coupler, M-1 1-(2,4,6-)lichlorophenyl)-3-(3-
(2,4-di-t-amylphenoxyacetamide 5-benzamide)-5-pyrazolone coupler, M-2゜4.4'-methylenebis(1-(2,4,6-)lichlorophenyl)-3-( 3-(2,4-di-t-amylphenoxyacetamido)penzand]-5-pyrazolone) coupler, CM-i 1-(2,4,6-)lichlorophenyl)-4-(1-
Naphthylazo)-3-(2-chloro-5-octadecenylsuccinimideanilino)-5-pyrazolone coupler, Y-1 coupler, n-1 Each sample prepared above was exposed to white light through a respective wedge. . After exposure, the samples 1 to 8
0 processed according to the following processing steps (Processing process) (Processing time) Color development
Bleach for 3 minutes and 15 seconds
6 minutes (fund) sand water washing
Fixed for 3 minutes and 15 seconds
6 minutes water washing 3 minutes 15 seconds stabilization 1 minute addition seconds The composition of the treatment liquid used in each treatment step is as follows.

Color developing solution composition: Bleaching solution composition: Fixing solution composition: Stabilizing solution composition: Next, the sharpness of the color image formed in the green light-sensitive emulsion layer of each sample was evaluated. The results are shown in Table 1.

In addition, the evaluation of the sharpness of the first one is MTP (Modulat
ionTransf@r Function) and compared the magnitude of MTF at a spatial frequency of 20°60/u.

(Table 1) As is clear from Table 1, sample 5 has the layer structure of the present invention.
In samples 2 to 8, it can be seen that the sharpness of the green-sensitive emulsion layer is significantly improved.In sample 2, the sensitivity of the blue-sensitive emulsion layer is significantly lowered due in part to the filtering effect of the colored coupler in the green-sensitive emulsion layer. 〇 has been improved. However, the green-sensitive emulsion layer deteriorates color purity due to asymmetric absorption (secondary absorption) in the blue to 500° range, resulting in loss of vividness and brightness, which is a serious problem in terms of color reproduction. It can be seen that Samples 516°7 and 8 of the present invention are excellent silver halide color photographic light-sensitive materials with significantly improved graininess and sharpness, and no decrease in color purity or photographic sensitivity.

Example-2 Among the samples used in Example-1', sample 1.2
.

(Processing...Relative humidity (R1() 75 cm, temperature 40
The sample is kept in a closed container for 17 hours in which an atmosphere is maintained at a formaldehyde gas concentration of 5×10 mol//. ) The results obtained are shown in Table 2.

(Table 2) As is clear from the results in Table 2, samples 5 to 8 prepared according to the present invention were all resistant to the adverse effects of formalin and had excellent raw sample preservation properties.

Agent Yoshimi Kuwabara Procedural Amendment 1, Indication of Case Patent Application No. 2148 of 1982 Name of Invention Color s'yt Material 3 Supplementary Relationship with the Case of the Person Patent Applicant Address Nishi-Shinjuku, Shinjuku-ku, Tokyo 1-26-2 Name (+271 Konishiroku Shasei Kogyo Co., Ltd. Representative Director Nobuhiko Kawamoto 4, Agent 191 Address 6, Konishiroku Shasei Kogyo Co., Ltd., Sakura-cho II, Hino-shi, Tokyo) The "Claims" section and the "Detailed Description of the Invention" section of the subject specification.

7. Contents of the amendment (1) The "Claims" of the 1ial document will be corrected as shown in the attached sheet.

(2) The "Detailed Description of the Invention" in the specification is corrected as follows.

(a) @Specifications page 10, line n to page 11, line U "represents a blocked coupler group that produces a reaction product. This magenta dye-forming property is preferable...reaction product Represents a blocking group that produces a reaction product.
represents the resulting blocked coupler group. ” (b)
14th page, line 9 to 1IIL page 15, line 2, typical couplers for 41IK by the author are as follows. In the above general formulas (III), CIV) and ①), the Cp group bonded to the coupling position represents a blocking coupler group, as described above, but preferably I A group inactivated by /Is is desirable.

Here, 11 is alkyl-0-CO-.

γ-alkyl-CO-, aryru-0-CO-, a9-h
-Co -* -COOII *-NQm or 10N
and V represents the group defined above for R' or the aryl-NHCO-ah group (wherein at least one of R@ and V represents one or more carboxylic groups, sulfonyl groups, or an aryl group substituted with a hydroxyl group).

The above-mentioned -CIO1'l'#'i is a capping group that is detached from the magenta dye-forming coupler group to produce a mobile reaction product after the reaction with the 1-formed color developing main group.

Next, representative couplers for @ according to the present invention are shown below. ”, (c) page 9, line 4, page 1, line 16 r*lI Showa 2515-17644
We have corrected the text ``Specification of No. No. 114946'' to ``Unexamined Japanese Patent Publication No. 114946/1983.''

2. Claims (1) On a transparent support, a red 5Jlt silver halide emulsion layer, a green light-sensitive silver halide emulsion layer, a yellow filter layer, a blue IIA layer, a sex halide emulsion layer, and a protection layer. The uppermost protective layer also serves as a yellow filter layer, and the sensitive halogenated chain emulsion layer, which is placed further away than the support, is an aromatic primary azun developing crude drug. The following general formulas (I) and (II) are capable of forming a magenta dye image by reacting with snow-transforming organisms.

A silver halide color photographic light-sensitive material characterized in that it substantially contains photographic couplers represented by GI[), GV) and ■).

General formula (1) (If) (n[)
qy) (V) [In the above formula, m'' and V are each an alkyl group, a monoyl group, a heterocyclyl group, an acyclyl group, an acylanno group, a hydroxy group, an alkyl group, an alkylthio group, a carboxy ifI or an esterified carmexyl group [where R'' represents an 11M water atom or a coupling-off group; In addition, in the above formula, Cp, which is single-bonded to the nitrogen atom forming the heterocycle, is an oxidized Represents a two-chain coupler group that produces a colorless or alkaline regenerating reaction product when the reaction with the color-forming Takisochurei occurs. (2) The silver halide color according to claim II, item 1, wherein the protective layer has a filter density of 50 mo or more of an all-yellow filter # device of the silver halide color photographic light-sensitive material. Photographic material.

(3) Claim 111g characterized in that the edge-sensitive silver halide emulsion layer disposed farthest from the support consists essentially of regular silver halide grains.
Silver halide color photographic light-sensitive material according to item 1.

Procedural amendment l Indication of the case Patent application No. 2148-2 Name of the invention Color photosensitive material 3 Relationship with the case of the person making the amendment Patent applicant address 24J, Nishi-Shinjuku +4', Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (+27) Representative Director of Roku Konishi Photo Industry Co., Ltd.
Makoto Kawamoto Shoten 1'fr 5, Sakura-cho, Hino-shi, Tokyo Date of Supplementary 17 Order Vol. 6, ``Claims'' column and ``Detailed Description of the Invention'' of the specification to be amended. 7. Contents of the amendment (1) The scope of the claims will be amended as shown in the attached sheet.

(2) Detailed description of the invention@e Amended as follows.

Attached claims (1) A red-sensitive silver halide emulsion layer on a transparent support,
It has a green-sensitive silver halide emulsion layer, a yellow filter layer, a blue-sensitive silver halide emulsion layer, and a protective layer e, and the uppermost protective layer also serves as a yellow film layer and is more suitable than the support. The installed green light-sensitive silver halide emulsion layer reacts with the oxidizing agent of an aromatic primary aionic developing agent to form mazemme dye Iliig II, which is represented by the following general formulas (I), (II), and (m). A silver halide color photographic light-sensitive material, characterized in that it substantially contains a photographic coupler represented by (1) and (2).

General formula (1) (II) (m) (IV)O ■) L;P [In the above formula, R1 and V are each an alkyl group, an aryl group, or a hetero4? It represents an acylamino group, an acylamino group, a hydroxy group, an alkoxy group, an alkylthio group, a carboxy group or an esterified carboxy group, and ILa represents a water bulk atom or a combining group.

In addition, in the above formula, Cp, which is single-bonded to the nitrogen atom forming the heterocycle, is a blocker that produces a colorless or alkali-labile reaction product after reaction with the oxidized color developing crude drug. The preferred magenta dye-forming Kabutsu group, representing the coupler group, is deactivated by a Cp group (cp is --CHR'R') attached to the coupling position.

Here, V in k is alkyl-co-, aryl-o-co-, aryl-4-Co-
1-cooH,-)lfo, or -α, and ml is the group defined above for R4< or a group representing aryl-NIICO- (where at least l11 is predominant among R4 and R1). or an alkyl group or an aryl group capped with or more than one carboxy group, sulfo group, or H)'Hoxy group.

It represents a capping group that is cleaved from the magenta dye-forming coupler group after reaction with a color developing agent to produce an aesthetic reaction product. ] (2) The protective layer is an all-yellow filter of the silver halide color photographic light-sensitive material.
The silver halide color photographic material according to claim 1, characterized in that it has 11 or more filters *t.

(3) The edge-sensitive silver halide emulsion layer located furthest from the support consists essentially of regular silver halide grains! ! l
The silver halide color photographic material according to item 1.

Claims (3)

[Claims] (1) A red-sensitive silver halide emulsion layer on a transparent support,
It has a green light-sensitive silver halide emulsion layer, a yellow filter layer, a back light-sensitive silver halide emulsion layer, and a protective layer, and the uppermost protective layer also serves as a yellow filter layer, and the layer furthest from the support. The green-sensitive silver halide emulsion layer placed on the substrate reacts with the oxidation product of the aromatic primary amine active agent to form a magenta dye image.
), (It), (Otori), ([V) and (V) A silver halide color photographic light-sensitive material 〇 General formula (1) (D ) % Formula % () [In the test, R1 and R8 are each an alkyl group, a ryyl group, a heterocyclyl group, an amino group, an acylamino group, a hydroxy group, an alkoxy group, an alkylthio group, a carboxy group, or an esterified carboxy group. , R'' represents a hydrogen atom and a coupling-off group. In addition, in the above formula, a single bond to a nitrogen atom forming a heterocycle or an oxidized color-forming herbal drug. represents a capped coupler group which, after reaction, produces a colorless or alkali-soluble reaction product.The Q group attached to the coupling position of each preferred magenta dye-forming coupler group is formed by the group -CHR'R@. In this case, R1 is alkyl-O-CO-, alkyl-CO-, aryl-0-CO-, aryl-Co-
, -C0OH, -No, or -CN, and all is the group defined in R1 above or -
-NHC (a group representing >- (where Bll and R6
at least one of them contains one or more carboxy groups, sulfo groups, alkyl groups or aryl groups substituted with tahyl and hydroxyl groups. R@ represents a capping group that detaches from the magenta dye-forming coupler group to form a mobile reaction product after reaction with oxidized color developing agent. ] (2) The silver halide color photographic light-sensitive material according to claim 1, wherein the protective layer has a filter density of 5096 or more of the total yellow filter + density of the silver halide color photographic light-sensitive material. material. (3) The halogenated silver halide emulsion layer according to claim 1, wherein the green-sensitive silver halide emulsion layer disposed farthest from the support essentially consists of regular silver halide grains. Silver color photographic material.