JPS59113437A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To obtain a high-sensitivity photosensitive material whose sharpness, picture keeping quality, and graininess are improved by incorporating a diffusion resisting compound which emits components that cause coupling reaction with oxidized bodies of a principal chemical of coloring development in a nonphotosensitive intermediate layer. CONSTITUTION:Plural silver halide emulsion layers which have substantially the same color sensitivity, but differ in photographic sensitivity are formed on a base, and a photosensitive layer containing a diffusion resisting coupler for photography is also formed on the base to obtain a photosensitive silver halide material. Then, the nonphotosensitive intermediate layer is provided adjacently to a silver halide emulsion layer having the highest photographic sensitivity among the plural layers on the base side. Further, the diffusion resisting compound which emit coupling components which couple with oxidized bodies of principal chemicals of coloring development by coupling reaction is incorporated in this nonphotosensitive intermediate layer. Consequently, the photosensitive material which has high sensitivity and provides good gradations while its sharpness, picture keeping quality, and graininess are improved is obtained by using a small amount of silver.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to silver halide photographic materials, and in detail, silver halide photographic materials with improved photographic properties such as sensitivity, graininess, sharpness, storage stability, and gradation. Regarding materials. [Prior Art] There has been a strong demand for the development of high-sensitivity, fine-grained photosensitive materials for silver halide photographic materials (hereinafter referred to as photosensitive materials), and for this reason, many improved photosensitive materials have been developed. Materials, particularly color photosensitive materials, have been proposed. One example of a photosensitive material suitable for the above purpose is British Patent No. 92&045 Specification 1. 1. a high-sensitivity silver halide emulsion layer (hereinafter referred to as a high-sensitivity emulsion layer) containing a diffusion-resistant coupler that develops color in substantially the same hue; By coating a low-sensitivity silver halide emulsion layer (hereinafter referred to as "low-sensitivity emulsion layer") with a silver halide emulsion of the same color sensitivity in separate layers, and further adjusting the pothole coloring density of the high-sensitivity emulsion layer to a low value. It states that sensitivity can be increased without deteriorating graininess. However, in recent years, the sensitivity of color light-sensitive materials for photography has become increasingly high, forcing the use of unrefined silver halide particles with poor graininess and/or couplers with high coupling speed in the silver halide emulsion layer. There is. For this reason, the method described in British Patent No. 923.045 Ming-a-Teng was found to be insufficient in improving the graininess, and further efforts have been made to improve the graininess. For example, Japanese Patent Publication No. 49-15495 states that multigraininess can be improved by providing a gelatin layer between the high sensitivity emulsion layer and the existing low sensitivity 411 layer. Although this method improves the graininess in the low-grained region, the shape of the gradation is significant. If the sensitivity of the low-sensitivity emulsion layer is increased by increasing , the graininess in the middle density range, which is particularly important in practice, deteriorates, which is undesirable. Historically, multilayer color photosensitive materials having the above structure have had the disadvantage that the stability of the color image density deteriorates over changes in development processing conditions, such as pH value, temperature, time, etc. It also has Furthermore, for example, Japanese Patent Application Laid-Open No. 57-155536 discloses that photographic diffusion resistance 1 lar and substantially a non-light-sensitive hydrophilic colloid layer containing a photographic diffusion-resistant coupler which develops colors to the same hue and whose coupling speed is not greater than the coupling speed of the photographic diffusion-resistant coupler contained in the high-sensitivity emulsion layer; It is stated that the graininess and gradation can be improved by providing this. There is no breakdown in gradation due to this method, and graininess is improved, but the improvement in graininess in the low to medium density range is still insufficient. For example, the above-mentioned Japanese Patent Publication No. 49-15495 and Japanese Patent Application Laid-Open No. 53-7
No. 230 discloses that medium-sensitivity silver halide emulsion layers with low coloring density are provided between the high-sensitivity emulsion layer and the low-sensitivity emulsion layer. A method is described in which a compound capable of releasing a development inhibiting substance (hereinafter referred to as a DIR compound) is contained. However, these methods have drawbacks such as increased fog due to the increased amount of silver halide used and increased power consumption of precious silver resources. Furthermore, in a light-sensitive material having two or more silver halide emulsion layers with the same color sensitivity, the silver halide emulsion layer with good crystal sensitivity generally improves graininess by lowering the slurry density. (In this case, the developing agent produced from the slow reaction diffuses into a wide range of lead in search of a partner to react with, forming a large pigment cloud with low concentration.
(which is considered not to worsen the graininess) is not confined only to the layer formed by the development of the silver halide of the silver halide emulsion layer having higher photosensitivity, and the oxidized product of the developing agent. It then diffuses into adjacent or adjacent silver halide emulsion layers of higher coupler density and lower sensitivity, where it forms a granular and conspicuous dye cloud. As a result, when viewing photosensitive materials, the developed silver grains of the silver emulsion layer, which have a higher photoresistance, extend to the problematic density (or photosensitive) region, resulting in deterioration of graininess. This results in the following drawback. [Object of the Invention] Therefore, the object of the present invention is to provide a photosensitive material which has high sensitivity, good gradation, and further improved sharpness, image storage stability, and graininess, and which requires less amount of photosensitive material. It is in. The following margins [Effects of the Invention] As a result of various studies by the present inventors, the above object is to provide a plurality of silver halide emulsion layers with substantially the same color sensitivity but different photosensitivity on a support. and at least one photosensitive layer containing a photographic diffusion-resistant coupler on a support, wherein at least one of the plurality of silver halide emulsion layers is the most photosensitive layer. A non-light-sensitive intermediate layer is provided adjacent to the support side of the silver halide emulsion layer having a high degree of brightness. A silver halide photographic light-sensitive material containing a diffusion-resistant compound capable of releasing a coupling component capable of causing a coupling reaction with an oxidized form of a color developing agent by causing a coupling reaction with an oxidized form of a main ingredient. I discovered what I could achieve. In other words, the present invention proposes a new and improved photosensitive material to solve the above problems. [Structure of the Invention] The photosensitive material of the present invention will be explained in more detail below. Before explaining the present invention, one embodiment of the present invention will be explained below. That is, in the present invention, for example, photosensitive layers having different photosensitivity, that is, a high-sensitivity emulsion layer and a low #1 degree milk 1+ layer are provided with the intermediate layer according to the present invention sandwiched therebetween. In this case, the high-speed emulsion layer and the low-speed emulsion layer each have 1
Although a layer may be used, it is preferable to use two or more layers because the effect of the method described in British Patent No. 923.045 can be added to the effect of the present invention. In addition, in the present invention, it is preferable that the high-sensitivity emulsion layer is provided farther from the support than the low-sensitivity emulsion layer, and when the high-sensitivity emulsion layer and the low-sensitivity emulsion layer each have a length of 27 m or more, It is preferable that the layer close to the support is a layer with low sensitivity.Also, the difference in sensitivity between the high-speed emulsion layer and the low-speed emulsion layer is determined at the optimum point in consideration of gradation and graininess. can be calculated using a well-known method, but in general, it is generally 0.1 to 1.0+, E(E
: exposure amount). Historically, the high-speed emulsion layer and the low-speed emulsion layer have substantially the same color sensitivity, and in a color developing tank and after processing, the two emulsion layers have substantially the same color sensitivity. It is preferable to contain a photographic diffusion-resistant turnip 2- which can form a coloring dye having a hue. Furthermore, the intermediate layer according to the present invention contains a diffusion-resistant compound capable of releasing a coupling component capable of causing a coupling reaction with the oxidized form of the color developing agent. (hereinafter referred to as the compound according to the present invention), but when the compound according to the present invention causes a coupling reaction with the oxidized product of the color developing agent and forms a coloring component as a result, the hue thereof is as described above. It is preferable that the hue be substantially the same as that of the coloring dye formed in the high-speed emulsion layer and the low-speed emulsion layer, or be colorless. In addition to the compound according to the present invention, the intermediate layer according to the present invention may contain other types of photographic diffusion-resistant couplers, hydroquinone derivatives for controlling the progress of development, colorless couplers, fine-grain silver halide, etc. It can also contain. Moreover, the intermediate layer can also be composed of two or more layers. In general, a photosensitive material containing Kabucy includes a red-sensitive silver halide emulsion layer containing Kabu2- for cyan coloring with photographic diffusion resistance, a green-sensitive emulsion layer containing Kabu2- for magenta coloring, and a coupler for yellow coloring. 1. In this specification, "substantially the same color sensitivity" means having a light sensitivity in substantially the same spectral region, red, green, respectively
In a broad sense, it refers to three divisions of blue, and slight spectral changes are considered to be substantially the same. Furthermore, when the photosensitive material according to the present invention is applied to each of the red-sensitive, green-sensitive, and blue-sensitive layers, remarkable effects related to the present invention are observed, but it is preferable that at least the green-sensitive layer exhibits the embodiment of the present invention. Furthermore, if the present invention is applied to all color-sensitive layers, the quality of the final color image will be even better. The amount of the compound according to the present invention contained in the above-mentioned intermediate layer according to the present invention is determined when a colored component is formed as a result of a coupling reaction with an oxidized product of a color developing agent. The maximum color density ratio of the intermediate layer and the low-speed emulsion layer according to the present invention is 1, with the maximum color density of the low-speed emulsion layer being 1, and the ratio of the high-speed emulsion layer and the non-light-sensitive intermediate layer is 0.02 to 0.7, respectively. , preferably 0.05 to 0.6
, particularly preferably from 0.05 to 0.2. It is believed that the color development of the compound according to the present invention contained in the intermediate layer according to the invention is due to the reaction with the oxidized product of the developing agent generated during development of the high-speed emulsion layer and the low-speed emulsion layer. In addition, when forming a substantially colorless coupling component as a result of the above coupling reaction, the amount added is not particularly limited, but preferably the upper limit is 8 x 10 mol/-1, and more preferably the upper limit is 3 x 10 mol/-1. The lower limit is approximately 1×10 mol/rrl. In the above embodiment, two or more compounds according to the present invention can be used in combination in the intermediate layer according to the present invention. When two or more compounds are used in combination, at least one of the compounds according to the present invention contained in the intermediate layer according to the present invention has the highest coupling speed among the photographic diffusion-resistant couplers contained in the high-speed emulsion layer. It is preferable that the coupling speed is the same or higher than that of the standard. Compounds according to the present invention that have a coupling speed equal to or higher than that of the photographic diffusion-resistant turnip 2- contained in the high-speed emulsion layer are suitable for use in the intermediate layer according to the present invention. It is preferable that 30 or more of the compounds according to the present invention other than those mentioned above and/or the various compounds mentioned above are contained, and it is particularly preferable that 70% or more of them are contained. Comparison of the coupling rates of CUB-2 and the compound of the present invention contained in the high-sensitivity emulsion layer and the intermediate layer of the present invention was carried out using a silver-no-logonide emulsion prepared by a method well known in the art. - Add 0.05 mol of the target coupler or the compound according to the present invention to 1 mol of silver rognide, and perform commonly known sensitometry. At this time, nine tests were carried out by comparing the amount of Kb quality image silver under the same exposure conditions after color development, without nickel silver treatment, and after the fixing treatment. The coupling speed is defined as a coupler used in a sample in which the amount of developed silver is less than 9m or a compound according to the present invention has a fast coupling speed. The method for adding Kab2- or the compound according to the present invention is to add 2 moles of the coupler or the compound according to the present invention to 4 moles of tricresyl 7-mole-7-ate, 5 moles of ethyl acetate,
After dissolving in a heating bath in a 0 mol mixed solvent, it was mixed with an aqueous gelatin solution containing sodium dodecylbenzenesulfonate, and then emulsified and dispersed in a high-speed rotating mixer, and then added to the silver emulsion. Let's go. Turnip 2-, which cannot be dissolved in the above mixed solvent, is dissolved in a solvent in which the high boiling point solvent and Turnip 2- are equimolar, and added after being emulsified and dispersed. Preferred compounds according to the present invention have the characteristics of having a large amount of developed silver produced by the above-mentioned coupling rate comparison method, and a low coloring compound concentration of the coloring component after the Kab1Nong reaction with the oxidized product of the coloring developing agent. What you have will be used to your advantage. The compound related to the non-invention is a compound that has both a diffusion-resistant coupler component and a scavenger component of an oxidized color developing agent in its molecule, and the compound has both a diffusion-resistant coupler component and an acid compound of an oxidized color developing agent. A reaction occurs first, and then the product of that reaction is a type that reacts with the acid form of the color developing agent as a cross-scavenger, and a reaction between the scavenger component and the oxidized form of the color developing agent occurs first. C,
The product of the reaction then reacts with the oxidized form of the color developing agent as a diffusion-resistant coupler. The above-mentioned λ scavenger compound or scavenger component scavenges the oxidized form of the color developing agent in the color photosensitive material during development, and a typical example is a coupling reaction with the oxidized form of the color developing agent, resulting in photographic properties. Products that have no adverse effects on the product, such as colorless compounds or force 2-
Examples include those that generate compounds that can flow out from photosensitive materials. Typical compounds according to the present invention include those represented by the following general formulas [■] to [■]. General formula [■] Diffusion-resistant coupler component-■ CH-R Coupler component-I In the formula, R represents a hydrogen atom, an alkyl group, or a phenyl group, and the diffusion-resistant coupler component-I couples with an oxidized form of a color developing agent. A residue obtained by removing the hydrogen atom of the active site from the diffusion-resistant Kab2- that can react to form a diffusion-resistant coloring dye,
Turnip 2 - Component - ■ removes the hydrogen atom at its active site from a coupler that can undergo a coupling reaction with the oxidized form of a color developing agent to form a diffusive chromophore or a colorless compound that does not substantially absorb visible light. Represents the removed residue. Here, Turnip 2-component-■ corresponds to the above-mentioned scavenger component. The compound represented by the general formula [1] is the diffusion-resistant type Kab2-Ingredient-I and Kab2-Ingredient-I, and the component that has a high reactivity with the oxidized form of the color developing agent is the first to react with the oxidized form of the color developing agent. react,
At this time, the bond between the component and CH--R is cleaved, and the remaining component then reacts with the oxidized color developing agent. General formula [''] In the formula, diffusion-resistant Kab2-component-■ is derived from a diffusion-resistant Kab2- which can form a diffusion-resistant chromophore by a coupling reaction with an oxidized form of a color developing agent. The coupler component -■ represents the residue excluding the hydrogen atom at the non-active site, and the coupler component -■ is the general formula [

It is synonymous with []. Here, the diffusion-resistant cup-component-a is initially inactive, but when the active coupler component-■ reacts with the oxidized form of the color developing agent, the bond with the cup-2-component-f is cleaved and becomes active. becomes. Further, the coupler component - (2) corresponds to the above-mentioned scavenger component. In the general formula [[], the diffusion-resistant coupler component -' is preferably bound to the active site of the coupler component 1 by an oxygen atom in the component. The bonding state with the carbon atom at the active site in 2-component-' is preferably as follows. [Coupler component-" In the formula, the diffusion-resistant coupler component-■ has the same meaning as the general formula CD, and the coupler component-" reacts with the oxidized form of the color developing agent to form a diffusive color-forming element. or represents a residue obtained by removing a hydrogen atom at an inactive site from a coupler that can form a colorless compound that does not substantially absorb visible light. When the active diffusion-resistant coupler component -■ undergoes a coupling reaction with the oxidized form of the color developing agent, the bond with the diffusion-resistant coupler component -■ is cleaved to become an active scavenger.Also, the coupler component -
I corresponds to the scavenger component mentioned above. In the general formula [1], the coupler component -U is preferably bonded to the active site of the diffusion-resistant coupler component -① via an oxygen atom in the component. Here, the bonding state between the oxygen atom and the active carbon atom in the coupler component is preferably as described above. C+C==C+mC-0 [C represents an active carbon atom, O represents the above-mentioned oxygen fragment, m is 0 or 1.] Kabun component-I and a in general formula [[] to [1]
As such, conventionally known coupler residues are used. Examples of the KAB-2- include phenol-type KAB-2-, naphthol-type couplers, pyrazolone-type KAB-2-1 open-chain ketomethylene couplers, and indanone-type couplers. The above coupler includes U.S. Patent No. 2.298,443.
No. 2,407,210, No. 2,875,05
No. 7, No. 048, 194, No. 3.265.50
No. 6, No. 147,928, and the specifications thereof. Farbkuppler-eine Literat
ubersicht”Agfa Mitteil,
ung (Band [) ["Farbukub 2-Eineriteraturüberlich" Agfamiitskuylung (Band [1)] pp. 112-126 (1961)
Benzoylacetanilide type Yellow Turnip 2-1 or pivaloylacetanilide type Yellow Turnip 2-1 described in U.S. Patent Nos. 2,369,489, 2.34λ703, and 2,311,082. , No. 2,600,788, No. 2,908,573, No. 3,152,896, No. 3,519,429 and the above-mentioned Agfa Mitteilung (
Various magenta couplers such as pyrazolone magenta Kab 2- and indacylon magenta couplers described in Band [) pp. 126-156 (1961), and U.S. Pat. No. 2,367.531, U.S. Pat.
, No. 730, No. 2.474, 293, No. 2,77
No. 2,162, No. 2,895,826, No. &00
No. 2,836, No. 3.034,892, No. 3.0
41,236 and the above Agfa Mit
tellung (Band [I) pages 156-175 (
1961) and phenolic couplers. Next, representative examples of compounds related to the present invention will be listed, but the present invention is not limited thereto. The following margins [Exemplary compounds] Compound - (11 t H Compound - (2) Compound - (3) Compound - (4) Compound - (5) Compound - (6) t Compound - (7) t t Compound - (9) Compound-(10 Compound (11) H2 (z Shiz Compound-(12) Compound-(14) t ShiL Compound-(15) t OOH Compound-(16) t H Compound-(17) t HC2H5 Compound-( 18) Compound (21) According to the present invention, a photosensitive compound comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity and having slightly different luminous intensities in the photosensitive phase family of the present invention. The layer can contain a photographic diffusion resistance 1 color that generates a diffusion-resistant coloring dye that gives a color tone corresponding to the color of each color. The photographic diffusion-resistant cyanide compound 2- is preferably a phenolic compound or a naphthol compound, for example, as disclosed in U.S. Pat. No. 2,369,929.
No. 2,434,272, No. 2,474,293, No. 895.826, No. 3253.924, &
No. 034.892, No. 3,311,476, No. 3.3
86.301, 3419.390, 3458.
No. 315, No. 3,476.563, No. 3,591,3
No. 83, etc., and methods for synthesizing these compounds are also described in each of these specifications. The photographic diffusion-resistant Magenta Kab 2- used in the present invention includes pyrazolone-based bizolotriazole-based,
Examples include compounds such as bi2zolinobenzimidazole and indacylon. Top 2 Zolon thread magenta turnip 2-
For example, U.S. Pat. No. 2,600,788 and 306
2.653, 3,127.269, &311,
No. 476, same & 419゜ No. 391, same & 519,42
No. 9, No. 3,558,318, No. 3,684,514
No. & 888.680, Japanese Patent Application Publication No. 49-29639
No. 49-111631, No. 49-129538, No. 50-13041, etc.; Virazolotriazole Magenta Kab 2- is disclosed in U.S. Patent No. L247,493, Belgian Patent @ 79452
Compound listed in r#2 in No. 5; Bi2zolinobenzimidazole system Magenta Kab 2- as Co., Ltd., U.S. Patent No. 3
．． No. 061,432, West German Patent No. 4156,111,
Compounds described in Japanese Patent Publication No. 46-60479; Furthermore, as Intazon a-based magenta turnip 2-, compounds described in Belgian Patent No. 769.11.6 can be advantageously used in the present invention. can. As the photographic diffusion-resistant Yellow Cub 2 used in the present invention, an open-chain ketomethylene compound has conventionally been used. - can be used. Furthermore, 2-equivalent type Yellow Kab 2-, in which the carbon atom at the coupling position is substituted with a substituent that can be removed during the coupling reaction, is also advantageously used. these? Il#'i
U.S. Patent No. λ875.057, U.S. Patent No. 3.265.506
No. 3,664,841, &408.194,
fiJ &447.928, Doujin No.277.155,
No. 3.415.652, Special Publication No. 13576/1976,
No. 48-29432, No. 48-66834, No. 49-10726, No. 49-122335, No. 50
28834, No. 50-132926, etc. together with the synthesis method. In the present invention, if necessary, Color Doka 12- can be used in combination with the above-mentioned photographic diffusion-resistant Kab 2-,
Diffusion resistance power for photography used as an example 2-Docyankabu 2
- Typical examples are those of butterfly, phenolic or naphthol conductors, such as U.S. Pat.
No. 21,908, No. 3,034,892, British Patent No. 1,255.111, %Open 111848-22028
No. 50-123341, No. 50-30135,
The synthesis method is described in US Pat. No. &476.563, etc. In addition, as the photographic diffusion-resistant force 2-do magenta coupler used in the present invention, a compound in which an arylazo-substituted compound is generally used at the coupling position of a force 2-res magenta coupler is used, for example, US Pat. , No. 171, No. 498 to No. 608, &01J
No. 5,712, No. 3,684,514, British Patent No. 9
No. 37,621, 'F'j open 18349-123625
No. 49-31448. It is also possible to use a type of colored magenta turnip 2- in which the dye flows out into the processing solution by reaction with the oxidized product of the 'fA(8) main ingredient, as described in U.S. Patent No. &419.391. can. In the present invention, the amount of the photographic diffusion-resistant coupler used is generally equivalent to 1 mo of silver in the light-sensitive silver halide emulsion layer.
2 x 10-' Mokfzi L5 x 10-”%
k, preferably from 5 x 10 mol to 5 x 10 mol for Fi sensitive emulsion layers, and 2 x 1 for low sensitivity emulsion layers.
0-2 moles to 3×10 moles. The amount in the middle 1st river layer according to the present invention is such that it does not inhibit the effect of the compound according to the present invention, that is, lXl0 mol/drI?
Or 8 x 10 mol/dry? , preferably 1
j4x6 10 mol/dd to 3 x 10 mol/d
n? may be added. As a method for dispersing the compound according to the present invention and other types of photographic diffusion resistance used in the present invention, P
ft'M'f4 Various methods such as alkaline aqueous dispersion method, solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method can be used, and appropriate methods can be used depending on the chemical structure of the photographic diffusion-resistant cutler. You can choose the right person. In the present invention, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. These dispersion methods are not well known, and the latex dispersion method and its effects are described in %Kokai No. 49-74538, No. 51-59943,
Publications No. 54-32552 and Research Disclosure,
August 1976, Volume 14850, pages 77-79. Suitable 2-texes include, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl acrylate, 2-acetoacetoxyethyl methacrylate), 2-
(Methacryloyloxy) ethertrimethylammoniummethosal7a), 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-infuq
Homopolymers, copolymers and terpolymers of monomers such as viracrylamide, N-(2-(2-methyl-4-ochinebentyl))acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, etc.Oil-in-water type As the emulsification dispersion method, a conventionally known method for dispersing a hydrophobic additive such as turnip 2- can be applied.
Even if the surfactant is dissolved in a single or mixed solvent of a high boiling point organic solvent with a boiling point of 175°C or higher such as nitricresyl phosphate and dibutyl phthalate and/or a low boiling point organic solvent such as ethyl acetate and butyl propionate, After mixing with an aqueous gelatin solution containing gelatin and then emulsifying and dispersing in a high-speed rotary mixer or colloid mill, the emulsified dispersion can be added directly into the silver halide emulsion layer or intermediate layer, or the emulsified dispersion can be mixed with a gelatin solution containing a low boiling point (by a known method). After removing the solvent, it is added to the silver halide emulsion or to the interlayer according to the invention. Furthermore, as colorless turnip 2- which can be used in combination with the present invention, British Patent Nos. 861,138, 914,145, and 1.
10 to 963, Japanese Patent Publication No. 45-14033, U.S. Pat.
Der Age 7a Rebelkiesen Volume 4, 352-36
You can choose from those listed in 7 Negative (1964), etc. In addition, in order to reduce the effects of the present invention, an oxide of a developing agent may be added to the high-speed emulsion layer, the low-speed emulsion layer, and/or the intermediate layer of the present invention sandwiched between these emulsion layers. A compound that reacts and releases a development inhibitor (hereinafter referred to as DIR)
It is called a compound. ) is preferably included. D.I.R.
For compounds, for example, U.S. Patent No. 3227.554
It is described in detail in Japanese Patent Application Laid-open No. 54-145135. The DIR compound is used in an amount of up to 2 q/di, particularly preferably from 0°1' to 0.9 q/d, relative to the above-mentioned constituent layers.
-Use in amounts up to. In addition to the above-mentioned embodiments of the present invention, the present invention is also preferably applied to a photosensitive material having at least one photosensitive M'e having three or more silver emulsion layers having different photosensitivity. Can be applied. For example, the photosensitive layer may include a silver norogonide emulsion layer with the highest photosensitivity on the side farthest from the support, an intermediate layer according to the present invention, and two or more layers with sequentially decreasing photosensitivity. A structure in which a silver emulsion layer is provided also exhibits the preferable effects of the present invention. Silver halides used in the silver emulsion layer of the light-sensitive material of the present invention include silver chloride, silver bromide, silver chloride, silver chlorobromide, silver chlorobromide, silver chlorobromide, and Any of those used in conventional halogenated No. 1 milking are included, such as mixtures thereof. These silver halide grains may be rice grains or fine grains, and the grain size distribution may be narrow or wide. 1
However, the crystals of these silver halide grains may be normal crystals or twin crystals, and any crystal with a [1oo] plane and a [111] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a no-shaped structure with different inside and outside. Further, these silver halides Fi may be of a type in which a latent image is mainly formed on the surface or a type in which a latent image is formed inside the grains. These silver halide grains can be prepared by methods known in the silver halide industry. It is preferable to remove the silver halide emulsion value soluble salts used in the present invention, but unremoved salts can also be used. It is also possible to use a mixture of two or more silver halide emulsions prepared separately. As the binder for the silver halide emulsion layer in the light-sensitive material of the present invention, conventionally known binders can be used. For example, gelatin is most preferred, and phenylcarba
It is also possible to use 2-ten derivatives such as acylated gelatin, acylated gelatin, and phthalated gelatin in combination. 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 the present invention are broadly classified into four types: noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers, and these can also be used in combination. 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 be used together. As the sulfur sensitizer, active gelatin #1 or a sulfur compound can be used.As the selenium sensitizer, active and inactive selenium compounds can be used.As the reduction sensitizer, active and inactive selenium compounds can be used. ] Tin salts, polyamines, bisalkylaminosulfides, silane compounds, isinoaminomethanesulfinic acid, hydrazinium hydrazine, and hydrazine derivatives. Various additives useful for light-sensitive materials such as stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, thickening agents, ultraviolet absorbers and others are used in the light-sensitive materials of the present invention. In addition to the silver halide emulsion layer and the intermediate layer according to the present invention, auxiliary layers such as an abdominal layer, an intermediate layer, a filter layer, an antihalation layer, a backing layer, etc. can be provided as appropriate. As the support for the material, conventionally known supports such as plastic film, 2-stick 2-laminated paper, baryta paper, synthetic paper, etc. may be selected as appropriate depending on the intended use of the photosensitive material. A subbing process is applied to strengthen the adhesion with the emulsion layer.Next, preferred embodiments of the main constituent layers of the Cassie photosensitive material layer according to the present invention are illustrated below.Arrangement of I (B) The order is written from the surface layer side to the support side. (Example 1) 1. Blue-sensitive 10-gen compound containing one or more layers of photographic diffusion-resistant Yellow Cub 2- A silver milk wound layer 2, a yellow filter layer 3 that absorbs color vision, a green-sensitive high-sensitivity emulsion layer 4 containing a photographic diffusion-resistant magenta cup, an intermediate layer 5 containing a compound according to the present invention, a photographic layer 5. Green-sensitive high-sensitivity emulsion layer 6 containing diffusion-resistant magenta turnip 2-; red-light-sensitive silver halide emulsion layer 7 containing one or more photographic diffusion-resistant cyan turnip 2- layers; support Body (Example 2) 1. One layer or two or more layers of a four-light blue silver halide emulsion layer containing a diffusion-resistant yellow turnip 2 for photography, a single yellow filter layer 3 that absorbs blue light, and one layer for photography. A green-sensitive low-sensitivity emulsion layer 4 containing a diffusion-resistant magenta coupler, an intermediate layer containing a compound according to the present invention & a green-sensitive emulsion layer containing a diffusion-resistant magenta power for photography 12- in a low density relative to the following layer 6: green-sensitive low-sensitivity emulsion layer 6 containing a photographic diffusion-resistant magenta coupler at an areal density relative to the layer 5; one layer or two or more layers of a photographic diffusion-resistant cyan coupler; A red light-sensitive silver halide emulsion layer 8 containing a support (Example 3) A blue light-sensitive silver halide emulsion layer containing a photographic diffusion-resistant yellow turnip 2- of 1.1@ or 2re or more Silver emulsion layer 2, green-sensitive silver halide emulsion layer 4 containing a photographic diffusion-resistant magenta coupler with one layer of yellow filter absorbing blue light & one layer and two or more layers of light, diffusion-resistant cyan cube for photography 2- 5, an intermediate layer 6 containing the compound according to the present invention, a red-sensitive low #containing emulsion layer 7 containing a photographic diffusion-resistant cyan coupler, and the above-mentioned support. Power of the present invention 2 - Photosensitive Material Co., Ltd. After exposure, an image can be obtained by a commonly used coloring dust imaging method. The basic processing steps include color development, bleaching, and fixing steps. Each of these basic processing steps may be performed independently, or two or more processing steps may be performed, or a single processing may be performed using a processing liquid that has these functions. Even if a one-bath color processing method containing a Fi color-forming imaging agent ferric salt part white component and a thiosulfate fixing component is used, or a diamine tetraacetate iron (2) complex salt bleaching component and a thiosulfate fixing component are used. This includes a one-bath marker fixing method, etc. Any processing method can be applied to the photosensitive material of the present invention. For example, typical methods include performing bleach-fixing treatment after color development, and further washing with water and stabilization treatment as necessary; A method of further washing with water and stabilizing treatment: or a method of pre-hardening, neutralization, color development, stop fixing, washing with water, deep whitening, fixing, washing with water, post-hardening, washing with water, color development, washing with water, supplementary color development. A method in which development is performed in the order of development, stopping, bleaching, fixing, washing, and stabilization; a development method in which the developed silver produced by color development is halogenated, and then redeveloped color development is performed to increase the amount of dye produced; Any method may be used for processing, such as a method for processing a low silver content light-sensitive material using an ayer agent such as an oxide or a cobalt complex salt. In the following margin, the compound of the present invention is described in the above-mentioned diffusion-resistant coupler for photographs other than the present invention, Wet β Kab 2-. Patent application filed by the same applicant, December 2-0, 1982.
Title of the invention: ``A compound capable of causing a coupling reaction with an oxidized product of a color developing agent to form a run-off type coupling product'' as shown in the specification of ``Silver rognide photographic light-sensitive material'' Diffusion-resistant coloring dye (produced from a photographic diffusion-resistant coupler contained in the high-sensitivity emulsion layer located far from the support side of the intermediate layer according to the present invention) through a coupling reaction with the oxidized form of the main ingredient. ) can be preferably used in the intermediate layer according to the present invention in combination with a photographic diffusion-resistant coupler (hereinafter referred to as a mobile coupler) capable of forming a mobile color-forming dye that develops substantially the same hue. The term "mobility" of such a mobile coupler means a degree of mobility that allows the coloring dye produced when it undergoes a coupling reaction with the oxidized form of a color developing agent to move within the layer containing the diffusion-resistant coupler. It is something to do. Such mobility can be controlled by the modulating group of the mobile coupler described below. The modulating group depends on the turnip 2-nucleus to which it is attached, other substituents introduced into the coupler, and the color developer used. Such a mobile coupler can be represented by the following general formula [IV]. General formula [1v] Coup-modulating group stabilizing group In the formula, Coup is a coupler core that generates a dye by a coupling reaction with an oxidized color developing agent, and the stabilizing group is a coupling group of the coupler core. It is a group that is bonded to the oxidized form of the color developing agent, and can cross from Cou, p to Flm during the coupling reaction between the 2- and oxidized color developing agents. The above-mentioned stabilizing group has a sufficient molecular size and shape to render Kabu2- non-diffusible. The regulating group is a group bonded to the non-coupling position of the coup, and controls so that the coloring dye produced by the coupling reaction between the coupler and the oxidized color developing agent becomes mobile as described above. This is the basis for Although the above coupe represents a turnip 2-matrix, it may be any coupler nucleus known or used in the art for coupling with oxidized forms of color developing agents to produce chromogenic dyes. The present invention will be illustrated with reference to examples below in the margins. Example 1 (1) Samples 1, 2, 3, 4, 5 and 6 were prepared by sequentially depositing the following layers on a support made of drawn cellulose triacetate film from the support side. K#-1 Layer-1...Green-sensitive, low-sensitivity, silver iodobromide emulsion containing 6 moles of silver iodide (average grain size 0.5μ, emulsion 1 mole) silver iodobromide emulsion containing 6 moles of silver iodide 0.25 mol, gelatin 40g
Emulsions 1 to 1 were chemically sensitized with gold and a small amount of sensitizer, and anhydrous 5°5'-dichloro-9-ethyl- was added as a green-sensitive sensitizing dye. 13'-
Di(3-sulfopropyl)oxacarbocyanine and droxide; anhydrous 5,5'-diphenyl-9-ethyl-&
3'-di(3-sulfopropyl)oxacarbocyanine: anhydrous 9-ethyl-&3'-di(3-sulfo7-robyl)-5,e, 5r6'-dibenzoxacarbocyanine hydroxide: was added, and then 4-Hydroxy-6-methyl-1,338,7-chitrazaindene 0.
25g, 1-phenyl-5-merkaftotet 2 sol 2
0q1 polyvinylpyrrolidone and the following dispersion (X-1) 5
00 Go was added, the green-sensitive sensitizing dye was adjusted, and the dry film thickness was 3. It was applied so that it became Oa. M-2: An aqueous gelatin solution for the intermediate layer was coated to a dry film thickness of 1.0 μm. Silver iodobromide emulsion containing 7 mol of silver iodide (average grain size o, 9 ps emulsion 1 to Todoro silver dihalide 0.25 mol) , 30g gelatin
) were adjusted in the usual way. This emulsion IKfff
i Chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-cyclo9-ethyl- as a green-sensitive sensitizing dye.
&3'-di(3-sulfopropyl)oxacarbocyanine hydroxide: anhydrous 5,5'-diphenyl-9-ether-3,3'-di(3-sulfopropyl)oxacarbocyanine; anhydrous 9-ethyl-3 ,3'-C(3-
sulfopropyl) -5,6,s:6'-dibenzooxacarbocyanine hydroxide: was added, followed by 0.25 g of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene, and 1-phenyl. 5 kg of -5-mercaptotetrazole and 0.2 gk of polyvinylpyrrolidone were added. Next, 200 tel of the following dispersion (X-2) was added thereto, and a green-sensitive, high-sensitivity silver halide emulsion was adjusted in VM and coated to a dry film thickness of 2.0 μVC. r+←〜4・・・・・−・Yellow filter Add gelatin aqueous solution in which yellow colloidal silver is dispersed to gelatin 0.9y/
m', silver 0.12g/rl? Dry film thickness 1.2μ at the ratio of
It was applied so that Sample)-2 The middle layer of Upper R Pi Sample 10 Layer-2 was prepared by adding the following dispersion (As) to the gelatin aqueous solution used for Layer-2 of Sample-1.
Sludge - t-octylhydroquinone 0.07g/I, applied to a dry film thickness of 1.0μ Sample-1
Sample 2 was prepared by self-adjusting and coating in the same manner as above. Sample-3 Sample-3 was prepared and applied in the same manner as Sample-2 except that the following dispersion (X-3) was added in place of the dispersion (As) used in Sample-20 Layer-2. Created. Sample-4 The following dispersion (M--4-) was added to the dispersion (AS) used for layer-2 of sample-2 above, and the sample was prepared and applied in the same manner as Fi sample-2. -4 was created. Sample-5 Sample-5 was prepared and coated in the same manner as Sample-2, except that the following dispersion (H-, 4-) was added instead of the dispersion (As) used for layer-2 of Sample-2 above. It was created. Sample 6 Sample 6 was prepared by cooling the following layers in sequence from the support side onto a support made of a subbed triacetate film. Layer-1: Green-sensitive low-sensitivity emulsion layer Same as Layer-1 of Sample-1 in Example-1. Layer-2...Dry layer-2 of sample-1 in middle layer implementation full-1 with a dry film thickness of 0
．． It was applied to a thickness of 5μ. Layer-3: Same as layer-2 of sample-5 in intermediate theory example-1. Layer-4: Same as Sample-60 Ex-2 in Intermediate Layer Example-1. Layer-5: Same as Kamen-3 of Sample-1 in Example-1. Layer-6...Yellow filter layer Same as Sample-1 to -4 in Example-1. The dispersions used in each of the above emulsion layers or intermediate layers were prepared as follows. Dispersion (X-1); Magenta Turnip 9-(M 1 ) 54 gs force 2
-Domagenta Cobra- (CM-1) 14g and the following D
0.5 g of IR compound (D-3), 0.5 g of DIR compound (D-1)
) O, sg as tricresyl phosphate (TCP) 68
Dissolved in a mixture of 280 yd of g% ethyl alcohol (KA), added to 500 d of gelatin containing 8 g of triisoglobilnaphthalene sodium sulfonate, emulsified and dispersed with a colloid mill and trowel, and 1,00 yd. (1-
Adjusted to. Dispersion (X-2): The following magenta turnip? -(M-1) 30 g and (M
2) 90gs Colored Magenta Turnip 2-(C
M-1) 12g and the following DIR compound (D-2)
0.3g to T CP 70 g -, F A 280
tut mixture, added to 7,5 Ningze 2 Ten 500ml containing 8 g of sodium triimpropylnaphthalene sulfonate, and emulsified and dispersed in a colloid mill.
, 000-. Dispersion (As): 2,5-di-tart-octylno-hydroquinone 50
g was dissolved in a mixed solution of 50 g of TCP and KA 100-,
Triinpropylna 7 Sodium talene sulfonate 6
The gelatin solution was added to an aqueous gelatin solution containing 500 grams of gelatin, and emulsified and dispersed in a colloid mill to adjust to 800 grams. Dispersion (X-3): 60g of the exemplified compound (8) of the present invention in TCP60gs EA
Dissolved in a mixture of 180- and 7,5-gelatin containing 8 g of sodium triimpropylnaphthalene sulfonate, emulsified and dispersed in a colloid mill,
I arranged it to OOO group. Dispersion (M-4): In place of the exemplified compound of the present invention (8), the exemplified compound of the present invention (7)
) was used, but was dispersed and adjusted in the same manner as the above dispersion (X-3). Dispersion (M-5): Dispersed in the same manner as the above dispersion (X-3) using Compound OG of the present invention 9+1 instead of Compound (8) of the present invention,
It was adjusted. Magenta turnip 2-(M-1); 1-(14,6-)lichlorophenyl)-3-(3-(
2,4-di-t-amylphenoxyacetamide) penzamide to 5-bi2zone magenta coupler (M-2
): 4.4'-methylenebis(1-(su4,6-)lichlorophenyl)-3-[3-(z,4-di-t-amylphenoxyacetamide)penzamide]-5-bi2zoa
) Colored magenta turnip 2-(CMI): 1-(2,4,
6-Dolichlorophenyl)-4-(1-naphthylazo)
-3-(2-chloro-5-oftatecenylsuccinimidoanilino)-5-vilazolone DIR compound (D-1): 2-(1-,yuni-3-tetrazolylthio)-4-
Octadecylsuccinimide-1-indanone DIR compound (D-2): 1-Hydroxy-N-(2-m-decyloxyphenyl)-4-(1-phenyl-3-methyl-4-(1
-Phenyl-5-tetrazolylthio)methyl]-5-pyrazolyloxy-2-naphthamide DIR compound! $(D3): 2-(2-amino-1,3,4-thiadiazolyl-5-
Thio)-4-octadecylsuccinimide-1-indanone The samples were each exposed to white light through a light wedge and then processed according to the processing steps described below. Treatment Step (38C) The composition of the treatment liquid used in each treatment step is as follows. Color developer composition: Add 0.14 g of sodium monochloride to 1 t of water. Bleach solution composition: 1. ,. 71 glacial acetic acid (add water to 11 and use ammonia water to pH 6.0)
Adjust to. Fixer composition: Adjust to 0. Stabilizing solution composition: Add water to make 11. Next, for the color images formed on each of the above samples, the same-day results of fog, sensitivity, and gamma were compared at 55°C and 10%.
The results of storage for 3 days under relative humidity conditions, as well as graininess and #iron properties were measured. The results are shown in Table 1. In addition, in the table, the gamma and graininess of the unit layer formed by force 2 are the measured values of the composite layer given white thermal light, and the graininess (RM
8) is the standard deviation of the variation in density value that occurs when scanning with a microdensitometer with a circular scanning aperture of 2.5μ.
Detection of the improvement effect of image sharpness expressed in ,000 times value 11 MTF (Modulation Trans
fer Function), and the spatial frequency is 10.
This was done by comparing the magnitude of MTF at 7 days and 30 bottles/mouth. As is clear from the results in Table 1 above, Samples 3, 4, and 5 according to the present invention compared with Comparative Samples 1 and 2 outside the present invention.
Samples No. 6 and 6 exhibited excellent properties in terms of storage stability, graininess, and sharpness. Such an effect was unexpected and surprising within the scope of the prior art. The following margins are funny.fl-2 Ky#+r, s and 9 were prepared by applying the following layers one layer from the support side onto a support made of subbed cellulose triacetate film. Sample-7 Layer-1...Green-sensitive, low-sensitivity emulsion disintegration Silver iodobromide emulsion containing 6 moles of silver iodide (average grain size 0.35μ,
Emulsion I (containing 0.25 mol of Ky dihalogenated button and 40 gft of gelatin) was prepared in a conventional manner, and this emulsion I
K9 was chemically sensitized with gold and iron sensitizers, and Juku et al. used anhydrous 5,5'-dichloro-9-ether-easy (3-sulfonorovir) oxacarbocyanine hydroxide as a green-sensitive sensitizing dye; Anhydrous 5,5'-diphenyl-9-ethyl-3,3'-c(3-sulfopropyl)
Oxacarbocyanine; anhydrous 9-ethyl-3,easy(3-sulfonolovir)-s, 6. sj6'-dibenzoxacarbocyanine and droxide: were added, and then 4-hydroxy-6-methyl-1,3,3aS7-titrazainfyO, 25 g11-phenyl-5-mer, 1
77') Sensitized emulsion A sensitized by adding 20+lv of tetrazole and 0.2 g of polyvinylpyrrolidone and a silver iodobromide emulsion containing 6 mol of silver iodide (average grain size 0.6μ)
, the emulsion IKf (containing 9 halogenated sO, 2 s mol, and 40 g of gelatin) was prepared by the usual method, and the above-mentioned sensitized emulsion A and the method of -1- were combined with the same sensitizer as the sensitizer. Using a stabilizer, emulsion A and sensitized emulsion B, which had been increased by Niji, were mixed at a ratio of 1:1. Next, h'J fractional dispersion X -1) 50 (l rxl 'fr near J+
] A green light-sensitive low-sensitivity emulsion il+ was applied to the film to give a dry film thickness of 3.0 μm. I threat-2・-・・・green photosensitive medium x<U9+-shavings) i
,'! Emulsion A shown in -1 and emulsion 1 mixed in the ratio of milk
200- was added thereto, and a green photosensitive sensitizing dye M'Jf2) was applied as a layer to give a dry film thickness of 1.5 μm. @-3・・・Dry film thickness of middle layer Ceratin water sap 1. Six fabrics were made so that the angle was θμ. 1 Hiro-4...Green feeling? 4 senses 11U breasts at the same time! Silver iodobromide emulsion containing 7 molar width of silver iodide (average grain size 0.9μ, milk yield IKg, silver halide 0.2
5 mol, containing 30 g of gelatin) was prepared in a conventional manner. This emulsion IKf was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5-dichloro-9-ethyl-3,3-di(3-sulfonate) was obtained as a green daylight sensitized product. anhydrous 9-ether-3,
3-di(3-sulfopropyl)-s, 6. s:6'
-dibenzoxacarbocyanine hydroxide; then 4-hydroxy-6-methyl-1,3,3a,
7-teto2zaindene (1,25g, 1-2enyl-5
- 5η of mercaptotetrazole and 042 g of polyvinylpyrrolidone were added. Next, this was added with the above 1Iij dispersion (X-
2) Added 200 m of green photosensitive high quality pre-coated material and coated it to a dry film thickness of 2.0 μm. Layer-5 - Yellow filter applied i'; Same as layer-4 of test 1-1 in Lee-1. Trial 1+-8 Layer-1...Green-sensitive low-sensitivity emulsion layer implementation 98-2
Same as layer-1 of sample-7 in . Layer-2... Green-sensitive medium-sensitivity emulsion layer Same as Az'7 2 of Z-h-7 in Practical Example-2. kmi3 --- Same as layer-2 of sample-5 in intermediate layer Example-1. Layer-4... Green-sensitive emulsion layer, actual layer t'
Same as layer-4 of @xq-7 in -2. N7t -5...Yellow filter island implementation f
Same as ruler 4 of sample-1 in ii-1. Sample-9 Layer-1...Low-sensitivity emulsion layer implementation name for green feel...J
Same as layer-1 of sample-7 in -2. J',・'v -2-=-middle r'il N hero 9::-
Same as layer-2 of sample-5 in 1. ti・-3・・・Green photosensitive medium sensitivity nipple 14 layers i
Same as layer-2 of sample-7 in heat treatment f+-2. Layer-4...Green light-sensitive severe M1 degree emulsion layer Mfit1
! Layers -4 and -1 of sample-7 in -2. 7m -5...Yellow filter further example (
Same as layer-4 of sample-1 in -1. The sample thus obtained was treated in the same manner as in Example 1,
As a result of evaluating the graininess and sharpness of green light sensitivity, comparative samples -
Compared to Samples 7 and 9, the sample of the present invention exhibited the effects of the present invention similarly to Example-1.

Claims (1)

[Claims] The support has a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities, and at least one light-sensitive layer containing a photographic diffusion-resistant coupler on the support. a silver halide photographic light-sensitive material [b], a non-photosensitive intermediate layer is provided adjacent to the support side of at least the silver halide emulsion layer having the highest photosensitivity among the plurality of silver halide emulsion layers; Furthermore, the non-photosensitive intermediate layer contains a diffusion-resistant compound capable of releasing a coupling component capable of causing a coupling reaction with the oxidized form of the color developing agent by causing a coupling reaction with the oxidized form of the color developing agent. )・A silver oxide photographic material.