JPS60118836A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a color silver halide color photosensitive material capable of preventing coloring fog, color mixing stains, etc, for a long term by incorporating a specified compd. as the scavenger of the oxidized product of a developing agent in a photographic constituent layer. CONSTITUTION:A compd. incorporated in at least one of photographic constituent layers, especially, in the color mixing-preventing layer between each color- sensitive silver halide emulsion layer is represented by formula I in which one of Y1, Y2 is a group represented by formula II; R is halogen, alkyl, aryl, acyl, carboxy, acylamino, carbamoyl, sulfonyl, alkylthio, or sulfamoyl; (n) is 0-5; and the other of Y1, Y2 is aryl. Said compd. is preferably, such as a compd. represented by formula III in which Ar is aryl, and R, (n) are each same as those in formula I . As a result, said compd. reacts with the oxidized product of a developing agent in development processing, and prevents said product from diffusing into the other photosensitive layers to cause coloring fog and color mixing stains, and even after storage for a long term, it retains its characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Technical Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material containing a compound capable of preventing color fading, mixed color staining, etc. It's about materials.

(b) Prior art and its problems In general, silver halide color photographic materials contain three types of halogens on a support that are selectively spectrally sensitized to be sensitive to blue light, green light, and red light. A silver oxide photographic emulsion layer is coated. For example, in a silver halide color photographic light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are generally coated in this order from the exposed side.
A markable yellow filter layer is provided between the blue-sensitive emulsion layer and the green-sensitive emulsion layer to absorb blue light transmitted through the blue-sensitive emulsion layer. Furthermore, between each emulsion layer, another intermediate layer is provided for a special purpose, and a protective layer is provided as the outermost layer. In addition, for example, in photosensitive materials for color photographic paper, generally a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are coated in this order from the side to be exposed, and each layer has a special layer, just like in photosensitive materials for color negatives. For this purpose, intermediate layers including an ultraviolet absorbing layer, protective layers, etc. are provided. It is also known to provide these emulsion layers in a different arrangement from the above, and instead of using a single layer of emulsion layers with different photosensitive areas, it is known that the emulsion layers have sensitivities in substantially the same photosensitive area for each color light. It is also known to use two or more types of photosensitive emulsion layers having the same composition. In these silver halide color photographic light-sensitive materials, exposed silver halide is developed using, for example, an aromatic primary amine compound as a color developing agent, and the resulting oxidized color developing agent and dye-forming properties are developed. A dye image is formed by reaction with Turnip 2-. In this method, cyan couplers of phenolic or naphthol type, 5-pyrazolone, pyrazolinobenzimidazole, pyrazolone triazole, indacylon or cyanoacetyl magenta couplers are usually used to form cyan, magenta and yellow dye images, respectively. and acylacetamide 9
Alternatively, a benzoylmethane yellow coupler is used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developer.

The dye image of the silver halide color photographic light-sensitive material obtained as described above is produced by the oxidized form of the color developing agent and the coupler not passing through the exposed silver halide during color development. This reaction often causes color fog (stain) and deteriorates the quality of the image.

In such a color coupler, a color developing agent is oxidized by oxygen in the air or oxygen dissolved in a solution, and during color development, a silver chloride emulsion of a color photographic light-sensitive material is produced. It occurs when a dye is formed by reacting with a coupler in an unexposed area where a silver image is not formed in a layer.
Another method is that in a color diffusion transfer image forming method using a color diffusion transfer film unit, the oxidized developing agent produced without the development of silver halide is a non-diffusible dye-releasing redox compound (DRR compound). ) and when a diffusible dye is released due to a redox reaction.

Furthermore, such a color-forming coupler appears as a color mixing power. That is, in a silver halide color photographic material having a laminated structure in which blue-sensitive, green-sensitive, and red-sensitive emulsion layers are respectively coated on a support, yellow, magenta, and cyan couplers are used in the color development process. A coupling reaction occurs with the resulting oxidized color developing agent, and in each layer, yellow,
Form magenta and cyan dye images. However,
Since the oxidized color developing agent has a small molecular weight,
Couplers and cups that diffuse into the layer existing therein and into other adjacent layers, and exist elsewhere in the same layer or in other adjacent layers, regardless of the correspondence between color sensitivity and color development. Ring reaction may occur, resulting in mixed color capri.

In order to prevent such color fogging and color mixing capri,
Conventionally, various substituted hydroquinone color-forming fog inhibitors (anti-staining agents, ant
A method of adding and blending a maintaining agent has been proposed.

For example, U.S. Pat. No. 2,360,290, U.S. Pat. No. 2,419,613, U.S. Pat.
No. 1, No. 3,960,570, etc., and U.S. Patent No. 3 regarding the method using monobranched alkylhydroquinone.
, No. 700,453, West German Patent Application (Of, S) 2,
No. 149,789, JP-A-50-156438 and JP-A No. 4
No. 9-106329. On the other hand, for an example using di-substituted hydroquinone, US Patent No. 2,72
No. 8,659, No. 2,732,300, No. 3,243
, No. 294, British Patent No. 752.146 and “Chemical
Abstracts, Vol. 56, 6367b, etc., and U.S. Patent 3 regarding di-branched alkylno-isoquinone.
, No. 700,453, No. 2,732,300, No. 3,
No. 243,294, above, “Chemical Abstracts”
Magazine, JP-A-50-156438, JP-A-53-952
No. 8, Japanese Patent Publication No. 54-29637 and Special Publication No. 50-212
It is described in No. 49 etc.

In addition, U.S. Patent No. 2,701 describes the use of substituted hyperquinone as a developing agent oxidized product scavenger.
, No. 197, U.S. Patent No. 2,710,801 and U.S. Patent No. 2,704,713, JP-A-55-43521,
They are described in JP-A-56-83742, JP-A-56-10344, JP-A-57-22237, etc., respectively. Further, JP-A-55-72158 discloses examples of phenol compounds in which the 2 and 5 positions are each substituted with a sulfonamide group.

Generally, it is considered desirable that the scavenger of oxidized developing agent used as a color-forming capri inhibitor satisfies the following conditions.

(1) The compound must be capable of reacting with the oxidized developing agent produced during development of silver halide. For example, an oxidized developing agent scavenger added to an intermediate layer disposed between at least two silver halide emulsion layers exhibiting different color sensitivities reacts with the oxidized developing agent generated during the development process, resulting in the development of the oxidized developing agent. There is a need to prevent the oxidized active ingredient from diffusing from one photosensitive layer to another.

(2) The oxidized developing agent scavenger should not have a substantial adverse effect on the development characteristics of silver in the silver halide emulsion even when added to the constituent layers of the silver halide photographic light-sensitive material.

(3) The developing agent oxidized product scavenger must be non-diffusive so as not to migrate between the constituent layers of the silver halide photographic material and cause photographically unfavorable side effects.

In addition, this substance should not substantially cause any photographically unfavorable side effects before, during, and after processing of the silver halide photographic light-sensitive material.

(4) Crystals do not precipitate within the emulsion layer during or after emulsion coating and deteriorate the quality of the coated product, and do not cause colored by-products due to oxidation reactions during coating or processing. thing.

(5) The removal efficiency of oxidized developing agent can be maintained at a high level over a long period of time. Further, during long-term storage, this developing agent oxidized product scavenger should not oxidize within the constituent layers of the silver halide photographic light-sensitive material to produce colored substances.

(6) When it reacts with the oxidized developing agent, it should not produce colored substances and cause color turbidity.

Ideally, an oxidized developing agent scavenger that is contained in a constituent layer of a silver halide photographic light-sensitive material to prevent color-forming capri and color-mixing capri should satisfy all of the above conditions. The above-mentioned various substituted hydroquinones have a problem in that they cannot maintain a high level of scavenger effect over a long period of time. In addition, the above-mentioned substituted phenols have the disadvantage that they are oxidized to produce colored products during the high-temperature, rapid development process, and they also tend to react with oxidized developing agents to form colored products. However, the present situation is that a satisfactory scavenger for oxidized developing agent has not yet been developed.

(C) Object of the Invention The present invention is based on the discovery of a compound that satisfies the above-mentioned conditions as a developing agent oxidized product scavenger and a method of using the compound.

The first object of the present invention is to provide an oxidized developing agent that does not adversely affect the development characteristics of silver halide even when added to photographic constituent layers, and does not migrate between photographic constituent layers and cause photographically undesirable side effects. An object of the present invention is to provide a silver halide photographic material containing a scavenger.

The second object of the present invention is to oxidize the developing agent so that crystals do not precipitate during or after emulsion coating and deteriorate the quality of the coated product, and oxidize during coating or processing to avoid producing colored products. An object of the present invention is to provide a silver halogenide photographic material containing a body scavenger.

A third object of the present invention is to provide a development method that can maintain the removal efficiency (scavenger efficiency) of oxidized developing agent at a high level over a long period of time, and that does not oxidize and produce colored products during long-term storage. It is an object of the present invention to provide a silver halogenide photographic light-sensitive material containing an oxidized main drug, sulfuric acid.

A fourth object of the present invention is to provide a photosensitive material containing an oxidized developing agent sulfur which reacts with the oxidized developing agent to reliably prevent color capri and mixed color staining. be.

Seven other objects of the invention will become apparent from the description provided below.

(d) Specific Structure of the Invention The present invention will be described in more detail below, but the scope of the present invention is not limited thereby.

As a result of various studies, the present inventors found that a silver halide photographic photosensitive material comprising at least one photographic constituent layer containing at least one compound represented by the following general formula CI) on a support. The present invention was completed by discovering that the above object can be achieved by using a material.

General formula CI) [However, one of X and Y! p, 0 (where ■ represents a halogen atom, an alkyl group, an aryl group, an acyl group, a carboxyl group, an acylamino group, a carbamoyl group, a sulfonyl group, an alkylthio group, or a sulfonamide group, and n represents an integer from O to 5. ) and the other represents an aryl group. ] Among the compounds represented by the general formula CI) in the present invention, preferred are compounds represented by the following general formula (n).

General formula (II) (wherein Ar represents an aryl group, and R and n have the same meanings as a and n shown in the above general formula CI). ) The aryl group represented by Ar in the general formula (II) is preferably an aryl group having 6 to 40 carbon atoms, and this aryl group may have a substituent, such as , no-rogen atom, hydroxyl group, alkyl group, aryl group, acyl group, carboxyl group, alkylcarbamoyl group, arylcalc dimoyl group, alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, alkylsulfamoyl group group, an arylsulfamoyl group, an alkylsulfonamide F group, a 7'J-lsulfonamide group, a cyano group, and the like. Preferred specific examples include phenyl &, p
-1” decylphenyl group, 2,4-di-jert-acylphenyl group, 0-1 decyloxyphenyl group, m-
Examples include hexylsulfonamidophenyl group.

Examples of the halogen atom represented by R in the general formula [■] include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. The alkyl group represented by R in the general formula CI) is preferably a linear or branched alkyl group having 1 to 40 carbon atoms, such as a methyl group, an ethyl group,
n-propyl group, isopropyl group, lobethyl group, t-
Butyl group, n, < methyl group, n-decyl g, t-decyl group, n-todecyl group, 5ec-dodecyl group, tert
-todecyl group, n-hexadecyl group, 5ec-hexadecyl group, tert-hexadecyl group, n-octadecyl group, 5eC-octadecyl group, tert-octadecyl group, and the like.

These alkyl groups may have a substituent, and examples of the substituent include a chlorine atom, a halogen atom such as a bromine atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkylsulfamoylcarbamoyl group, etc. , arylcalc 2-moyl group, 1-nol group, cyan group, etc. Preferred examples @1 include 4-chlorobutyl group, 2-human 90xethyl group, 3
Examples include -methoxypropyl group, 3-n-butylsulfamoylpropyl group, and benzyl group.

Further, as the aryl group represented by R in the general formula CI), the same aryl group as the aryl group represented by A in the general formula (I[) can be used.

The acyl group represented by R in the general formula [■] may be, for example, an acetyl group, a hexanoyl group, a decamyl group,
Furthermore, examples of the carboxyl group include ethoxycarbonyl group, butoxycarbonyl group, and 1-decyloxycarbonyl group, and examples of the carbamoyl group include dimethylcarbamoyl group, di-n-octylcarnomimoyl group, and acylamino group. For example, 2
,4-di(tl-acylphenoxyacetylamino group, sulfonyl groups include, for example, decanesulfonyl group, hexadecanesulfonyl group, and sulfonamide groups include, for example, methylsulfonamibi group, octylsulfonamide group, tetradecyl group. sulfonamibi group,
Further, examples of the alkylthio group include an alkylthio group having a linear or branched alkyl moiety having 1 to 16 carbon atoms, such as an ethylthio group and a decylthio group.

The compound according to the present invention is added to a photographic constituent layer consisting of a light-sensitive halogen recording emulsion layer or a non-light-sensitive hydrophilic colloid layer of a halogenated photographic light-sensitive material. This compound is preferably non-diffuse in the photographic constituent layer. Therefore, the total number of carbon atoms in the compound represented by the general formula CI) is preferably at least 18, more preferably from 24 to 45.

Among the compounds represented by the general formula CI) of the present invention, particularly preferred are those in which 几 in the above general formula (1) is an alkyl group having 4 to 20 carbon atoms, an acylamino group having 6 to 25 carbon atoms, or an alkylsulfonamide group. , n is 1 or 2.

Next, specific examples of the compounds of the present invention will be shown, but the present invention is not limited thereto.

Exemplary Compounds (1) (3) (4) (5) (6) Next, synthesis examples of the compounds of the present invention will be described, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Exemplified Compound (2) u (A) (B) (2) Amytol 20. Solution of Of in pyridine 100- K p-(sec)-)'7'Silzenesulfonyl chloride (B) 70. Or is pyridine 100-
A solution dissolved in water was added dropwise in a nitrogen stream over 2 hours. After the addition was completed, the mixture was stirred for 5 hours. The reaction solution was diluted with 2N-HCI.
Add to the aqueous solution and filter the precipitated solid, wash with water and then acetonate)
Dissolved in IJ and treated with activated carbon, then recrystallized to form a white powder.
Exemplary compound (2) (melting point 142-146C) 42.1S
I got an F.

Elemental analysis value CHN8 Calculated value 68.06 B, 70 3.78 8.65 Analysis value 68.15 8.79 3.88 8.58 Synthesis example 2 Synthesis of exemplified compound (6) (C) (DJ 2-amino 30.Of -4-ditrophenol and 28.Or of benzyl chloride were added to 300 - of an ethanol solution containing 12.1f of potassium hydroxide and heated under reflux for 4 hours.

The reaction solution was distilled off under reduced pressure and concentrated to 500% water, and the precipitated solid was filtered, washed with water, and then recrystallized from acetonate IJ to obtain yellow powder 2-benzyloxy-5-nitroaniline (2-benzyloxy-5-nitroaniline). M point tz9-135tll') 26.1f was obtained.

Step 2 Blue. .

(D) (B) (F) 12.2 r of the product (D) and 17.5 t of p-r decylbenzenesulfonyl chloride r(n) were added to pyridine 20081 and heated under reflux for 8 hours. The reaction solution was poured into a 3N-HC7 aqueous solution, and the precipitated solid was filtered.
After washing with N-HC, ff aqueous solution and water, recrystallization with acetonitrile-ethyl alcohol yields a yellow powder of N.
-(2-pencyloxy-5-nitro)pheni/l/
-p-dodecylbenzenesulfonamide)” CF)
Obtained 18.8 ff.

Margin below Step 3 (F) (01 The said product (Fl 10.2 P THElooI11
0.51 of a 5% Pd/C catalyst was added to the /dreta solution, and the hydrogenation reaction was carried out at room temperature. 4 hours later, after confirming that the original thorn is gone, 6N-〇〇l! Added to 30M water bath solution. After filtering the reaction solution, the brown solid 2-
(4-)”decyl)-benzenesulfone amiibee 4-
9.91% of amino-phenol hydrochloride was obtained.

Step 4 (G) (HI (Exemplary Compound 6) Add p-toluenesulfonylchloride to a solution of the above product (G) 8.5 F in pyridine 6o-)" 3.
81 was dissolved in 2 lysine 15/2 and added dropwise at 4 oc.

After continued stirring for 3 hours, the reaction solution was poured into 3N-HC/aqueous solution. The precipitated brown solid was filtered, washed with water, and then treated with acetonate (dissolved) and treated with activated carbon, then recrystallized to give a white powder (exemplified compound +61') (melting point 155-158).
c) 6.62 was obtained.

Elemental analysis value CHN 8 Calculated value 62.18 6.40 4.68 10.71
Analysis 1st shift 62.31 6.49 4.78 10.6
5 or less margin The compound according to the present invention is preferably added to a non-photosensitive hydrophilic colloid layer of a silver halide photographic light-sensitive material.

This non-photosensitive hydrophilic colloid layer includes, for example, an intermediate layer, a filter layer, a surface protective layer, a color mixing prevention layer, and the like.

In a preferred embodiment of the invention, the compound according to the invention (oxidized developing agent scavenger) is added to an intermediate layer between the various emulsion layers.

In this case, it is preferably added to an intermediate layer between emulsion layers having different color sensitivities, or added to an intermediate layer between emulsion layers having substantially the same color sensitivity but different sensitivities. It is also preferable if Moreover, the compound according to the present invention is
It may be added to the silver halide emulsion layer. Furthermore, the compound according to the present invention can be added to non-photosensitive hydrophilic colloid layers other than the intermediate layer, such as filter layers and surface protection layers. Further, such a compound may be added to both the non-photosensitive hydrophilic colloid layer and the photosensitive silver halide emulsion layer.

The amount of the compound according to the present invention added to these layers is not particularly limited since the compound is substantially colorless and does not have any adverse effects such as coloring or staining by itself. In a preferred embodiment, when the compound according to the invention is added to the intermediate layer, the amount is about 1 my/rr? It can be used in the range from 1,0 OOV-.

In particular, when the intermediate layer is between emulsion layers with different color sensitivities, the range is from 501 mf/n to 500 mf/n? is preferable, and in the case of an intermediate layer between emulsion layers having substantially the same color sensitivity, it is 5q/ba to 200nl/n'? A range of is preferred. In addition, when adding this compound to the light-sensitive diameter silver halide emulsion layer,
3 x 10-1' color per mole of silver halide 3 x 1
It is preferable to use it in the range of 0-1 mol.

Furthermore, there is no problem even if two or more of the compounds according to the present invention are used in combination. In this case as well, the same amount as mentioned above is sufficient.

In order to introduce the compound of the present invention (developing agent oxidized product scavenger) into the photographic constituent layer of a silver halide photographic light-sensitive material,
Known methods such as those described in US Pat. No. 2,322,027 can be used.

For example, the compound according to the present invention may be used as a phthalic acid alkyl ester (e.g., dibutyl tucrate, dioctyl heptatarate, etc.), a phosphoric acid ester (e.g., triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.) , citric acid esters (e.g., acetyl tributyl citrate, etc.), benzoic acid esters (e.g., octyl benzoate, etc.), alkylamides (e.g., diethyl laurylamide), fatty acid esters (e.g., dibutoxydiethyl succinate, dioctyl azelate, etc.) ), and/or boiling point from 30°C to 150°C
Dissolved in one type of solvent or a mixed solvent of two or more types of organic solvents, such as ethyl acetate, propionate, propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. It is then dispersed into hydrophilic colloids.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-599
The latex dispersion method described in No. 43 can also be used.

The compounds of the present invention can be used in various silver halide photographic materials. Such silver halide photographic materials include black and white, color and pseudocolor silver halide photographic materials, and specifically include general black and white, printing black and white, X-ray, and electronic Line, high resolution, black and white
It can be applied to silver halide photographic materials, general color photographic materials, color X-ray photographic materials, and diffusion transfer type color silver halide photographic materials.

The hydrophilic colloid in the non-photosensitive hydrophilic colloid layer is
Gelatin is mainly used.

The gelatin used in the present invention is so-called alkali-treated (lime-treated) gelatin, acid-treated gelatin, or r Bul
l Soc Set Photo Japan JAI
6. Any enzyme-treated gelatin such as that described on page 30 (1966) may be used. Furthermore, partially hydrolyzed low molecular weight gelatin can also be used.

In addition, colloidal albumin, casein,
Cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate,
Sugar derivatives such as starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, vinyl pyrrolidone, polyacrylic acid copolymers, polyacrylamide, or derivatives/partial hydrolysates thereof, etc. may be used in combination.

In the present invention, the non-photosensitive hydrophilic colloid layer may contain gelatin hardener, surfactant, polymer latex,
Matting agents, dyes, ultraviolet absorbers, anti-fading agents, plasticizers,
It is possible to contain lubricants, antistatic agents, etc.
Regarding these additives, please refer to Research Disclosure 17.
The description in Vol. 6, pp. 22-28 (December 1978) can be referred to.

Further, as the silver halide used in the light-sensitive emulsion constituting the silver halide emulsion layer of the present invention, silver halide such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Any used in silver photographic emulsions are included.

The silver halide emulsion used in the multilayer silver halide color photographic light-sensitive material of the present invention can be produced by various conventional manufacturing methods, such as the method described in Japanese Patent Publication No. 7772/1983, or the method described in U.S. Pat. No. 2.592. , No. 250, that is, the so-called conversion emulsion manufacturing method or the so-called Lippmann emulsion manufacturing method, etc., and this silver halide emulsion can be prepared using a conventionally known chemical sensitizer. can be used.

In addition to chemical sensitization, this emulsion can be reduced sensitized with a reducing agent, and this emulsion can also be used with wetting agents, plasticizers,
It may contain film property improvers and the like, and may further contain various photographic additives such as coating aids, fluorescent brighteners, and antistatic agents.

Known 2-equivalent couplers and 4-equivalent couplers are used in the silver halide photographic material of the present invention. Among these couplers, examples of yellow couplers include open-chain acylacetamide couplers (e.g., bivallylacetanilides, benzoylacetanilides), and magenta couplers include 5-pyrazolone couplers and pyrazolobenzimidazole couplers. and pyrazolotriazole couplers, indasilone couplers and the like. Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible couplers having a hydrophobic group called a ballast group in the molecule. Colored couplers that have a color correction effect or couplers that release a development inhibitor with the degree of development (so-called DIR) are also used.
In addition to DIR couplers) or DIR couplers, it is also possible to use colorless DIR coupling compounds in which the product of the coupling reaction is colorless and releases a development inhibitor.

These couplers are generally used in amounts ranging from 2 x 10'' moles to 2 moles per mole of silver in the emulsion layer, preferably I x
10-2 moles to 5 x 10-' moles are added.

The coupler can be introduced into the silver halide emulsion layer using known methods, such as the method described in U.S. Pat. No. 2,322,027.

Also, Time No. 11851-39,853, JP-A-51-5
The polymer dispersion method described in No. 9.943 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The pH of the color developing solution used in the silver halide photographic light-sensitive material of the present invention is 8 or more, preferably pH 9 to 1.
It is 2. This color developing solution contains an aromatic primary amine color developing agent or a compound having a primary amine group on an aromatic ring and capable of developing exposed silver halide. The obtained precursor is preferably used.

Aromatic primary amine color developing agents include p-phenylenediamine derivatives, specifically 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N -diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N- Ethyl-N-
β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethyl-
4-amino-N,N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N
-β-methoxyethylaniline, 3-acetamide-4
-Amino-N.

N-diethylaniline, 4-amino-N, N-dimethylaniline, N-ethyl-N-β-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl -N-β-(β-methoxyethoxy)ethyl-3-methyl-4-amineaniline, and salts thereof such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. Moreover, various additives can be added to these color developing solutions as necessary.

The silver halide photographic material of the present invention is subjected to color development treatment after imagewise exposure.

The color development process is carried out by a normal color development method.

That is, first, it is processed with a color developing solution containing a color developing agent. Alternatively, a color developing agent or its precursor is contained, and this is treated with a so-called activator liquid.

Thereafter, a bleaching step and a fixing step are usually performed according to conventional methods.

This treatment may be done simultaneously with fixing or separately.

This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary. Various compounds can be used as bleaching agents, and various additives including bleaching accelerators can also be added.

The present invention is realized in various forms of silver halide color photographic light-sensitive materials. For example, the above-mentioned silver halide color photographic light-sensitive material may be an internal silver halide color photographic light-sensitive material containing a coupler, or an external silver halide color photographic light-sensitive material containing a coupler in a developer. In particular, coupler-containing internal silver halide color photographic light-sensitive materials are advantageous, and after exposure, color development is performed by a color development method. Furthermore, the coupler and the color developing agent are protected so that they do not come into contact with each other when unexposed and are present in the same layer, and are used in silver halide color photographic light-sensitive materials where they can come into contact with each other after exposure, or silver halide colors containing couplers. In a photographic light-sensitive material, a color developing agent is contained in a layer that does not contain the coupler, and when an alkaline processing solution is permeated, the color developing agent is moved and brought into contact with the coupler. There may be. Furthermore, the compound represented by the general formula (I) according to the present invention can also be used in a silver halide color photographic material for diffusion transfer by adding it to the photographic constituent layers of the light-sensitive material.

Common developing agents for color diffusion transfer include hydroquinones, aminophenols (e.g. N-methylaminophenol), pyrazolidones [e.g. phenidone (1-phenyl-3-pyrazolidone), dimezone (1-
phenyl-4,4-dimethyl-3-pyrazolidone), 1
-phenyl-4-methyl-4-oxymethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-oxymethyl-3-pyrazolidone], and the like.

In the reversal process, the image is developed in a black and white negative developer, then exposed to white light or treated in a bath containing a capri agent such as a ferroboron compound, and then color developed in an alkaline developer containing a color developing agent. At this time, there is no problem in including a capri agent in an alkaline developer containing a color developing agent. After color development, the silver is bleached with a bleaching solution containing ferricyanide or a ferric salt of aminopolycarboxylic acid as an oxidizing agent, and then fixed with a fixing solution containing a silver salt bath agent such as thiosulfate. The image and residual silver halide are removed, leaving a dye image. Instead of using a bleaching solution and a fixing solution, bleach-fixing can also be carried out using a one-bath bleach-fixing solution containing an oxidizing agent such as a ferric salt of aminopolycarboxylic acid and a silver salt bath agent such as thiosulfate. . Further, various treatments such as pre-hardening, neutralization, water washing, stopping, and stabilization may be performed in combination with color development, bleaching, fixing, or bleach-fixing. In particular, the processing steps in which the silver halide color photographic light-sensitive material containing the compound according to the present invention represented by the general formula (I) is advantageously processed include, for example, color development, washing with water, bleach-fixing, and washing with water if necessary. , stabilization and dry kneading as necessary, and these processing steps are carried out at a high temperature of, for example, 30° C. or higher and within an extremely short period of time.

In addition to the above-mentioned color developing agent, certain additives are added to the color developing solution as necessary. Main examples include alkali metal and ammonium hydroxides, carbonates,
Alkaline agents such as phosphates, buffers such as acetic acid and boric acid, pH
These include regulators, development accelerators, anti-capri agents, anti-stain or sludge agents, interlayer effect accelerators, preservatives and the like.

Bleaching agents used in bleaching include ferricyanide such as red blood salt, dichromate, permanganate, hydrogen peroxide, saran powder, and aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and iminodiacetic acid. Metal complex salts of polycarboxylic acids such as malonic acid, tartaric acid, and malic acid, ferric chloride, and the like are used alone or in combination as necessary. Various additives such as bleaching accelerators can be added to this bleaching solution as needed.

Fixing agents used in the fixing process include thiosulfate salts such as sodium thiosulfate and ammonium thiosulfate, and cyanide urinary conductors. You can also add

The silver halide photographic light-sensitive material containing the compound represented by the general formula CI) of the present invention is processed into a color developing agent containing both a primary aromatic amine color developing agent and an oxidizing agent for subjecting the metallic silver image to a redox reaction. It is also effective to treat using

When these color developers are used, the color developing agent is oxidized by an oxidizing agent and then coupled with a photographic color coupler to form a dye image. Such a color developing solution is disclosed, for example, in Japanese Patent Application Laid-open No. 48-9,729, and the preferred oxidizing agent for this purpose is a konol complex salt having a coordination number of 6. Color photographic processing involving a liquid is particularly effective for so-called silver-saving color photographic materials, which have a lower amount of silver than ordinary silver halide color photographic materials.

Further, the silver halide color photographic light-sensitive material containing the compound represented by the general formula [1] according to the present invention is preferably developed in a color developing solution containing a first aromatic amino color developing agent. is received into the photosensitive layer during the color development step and is added to the amplifying bath.
th) by means of a color photographic processing method consisting in the presence of a color developing agent transferred into the film and in contact with an intensifying solution containing an oxidizing agent as described above, for example a cobalt complex having a coordination number of 6. It is also useful. Another preferred oxidizing agent for this purpose is hydrogen peroxide solution.

Next, a typical example of a color development process that can be used for processing when the present invention is used as an internal color negative light-sensitive material will be shown.

[Processing process]

Processing step (33°C) Processing time The composition of each processing solution that can be used in the processing step is as follows, for example: [Color developer composition] [Bleaching solution composition] [Fixer composition] [Stabilizing solution composition] Next, a typical example of a color development process that can be used when the present invention is used as an internal color positive light-sensitive material will be shown.

[Processing process]

The composition of each treatment liquid that can be used in the above treatment steps is as follows, for example.

[Color developer composition]

[Bleach-fix solution composition] [Stabilizing solution composition] (e) Specific Examples of the Invention The present invention will be explained in more detail by describing Examples of the present invention below, but the present invention does not extend to these Examples. It is not limited.

Example 1 Coating samples 1 to 25 were prepared by sequentially coating the layers shown below from the support side onto a cellulose triacetate film coated with nine layers of a normal undercoat.

Layer-1: Antihalation layer with black colloidal silver dispersed in gelatin (dry thickness 2.0μ) Layer-2: Gelatin intermediate layer (dry thickness 1.0μ) Layer-3: Red-sensitive low-sensitivity emulsion layer 6 Silver iodobromide emulsion containing silver iodide of Morch (average grain size 0.3
μ, 100 f of silver halide per kg of emulsion.

(containing 70t of gelatin) was prepared in a conventional manner.

To 1 kf of this emulsion, a red-sensitive spectral sensitizer was added to a 0.1% methanol solution 210-, and as a stabilizer a 5% aqueous solution of 4-hydroxy-6-methyl-1,3+3a+7-titrazaindene 20- and cyanogen according to the following formulation. 400f of coupler emulsion (1) and 20f of emulsion (2)
01 were added respectively.

Furthermore, 30 ml of a 2% methanol solution of bis(vinylsulfonylmethyl)ether as a gelatin hardener was added to form a red-sensitive, low-sensitivity silver halide emulsion, and this solution was coated to a dry film thickness of 3.0 μm.

Composition of emulsion (1): ■ 10% by weight gelatin aqueous solution 1000f■ After dissolving the mixture at 55°C, the above 10 which had been heated to 55°C in advance
It was added to an aqueous gelatin solution of % by weight and emulsified using a colloid mill.

-1 Composition of emulsion (2): (1) A mixture of 10% by weight gelatin aqueous solution (100%) was dissolved at 55°C, and then added to the gelatin aqueous solution (2) previously heated to 55°C and emulsified in a colloid mill.

C-1 Layer-4 = Red-sensitive high-sensitivity emulsion layer The following changes were made to the silver halide emulsion liquid of Layer-3.

The silver halide solution prepared in this way has a dry film thickness of 2,
It was applied to a thickness of 4μ.

Layer - 5-layer color mixture prevention layer Emulsion containing developer oxidized product scavenger (3)
The dry film thickness is 1. It was applied so that θμ.

Composition of emulsion (3): (1) A 10% by weight gelatin aqueous solution 1000 r of the mixture was dissolved at 55°C, and then added to the gelatin aqueous solution (2) previously heated to 55°C and emulsified in a colloid mill.

lN-6: Green-sensitive low-sensitivity silver halide emulsion layer 11cf of the silver iodobromide emulsion used in layer-3 was added with green-sensitive spectral sensitizing dye o,
220 d of an i weight % aqueous solution was added, and 3,201° of a magenta coupler emulsifier (4) and 502° of a magenta coupler emulsifier (5) according to the following formulation were added, respectively. Furthermore, a 2% methanol solution of the gelatin hardener tositehis(vinylsulfonylmethyl)ether was added to prepare a green-sensitive and low-sensitivity silver halide emulsion. This liquid was applied to give a dry film thickness of 3.0 μm.

Composition of emulsion (4): (1) A mixture of 10% by weight gelatin aqueous solution (100%) (2) was dissolved at 55°C, then added to the gelatin aqueous solution (2) previously heated to 55°C, and emulsified using a colloid mill.

-1 0M-1 Composition of emulsion (5) 2. 10% by weight gelatin aqueous solution After dissolving the mixture of 1ooor.■ at 55°C, add it to the gelatin aqueous solution of Emulsified.

Layer-7: Green-sensitive high-sensitivity silver halide emulsion layer The following changes were made to the silver halide emulsion t- of layer-6.

The silver halide solution prepared in this way has a dry film thickness of 2.
It was applied to a thickness of 5μ.

Layer-8: Yellow colloidal silver layer (dry film thickness 0.7μ) Layer-9
: Blue-sensitive low-sensitivity silver halide emulsion layer 0.1 kg of blue-sensitive sensitizing dye is added to 1 kg of the same silver iodobromide emulsion as that used in layer-3.
180% by weight aqueous solution was added, and 1400% of yellow coupler emulsion (6) according to the following formulation was added. Further, as a gelatin hardener, 50 parts of bis(vinylsulfonylmethyl)"ether (7) 2% by weight water was added to prepare a blue-sensitive, low-sensitivity, halogen ratio silver emulsion. This solution had a dry film thickness of 3.
It was applied so that the thickness was 0μ.

Composition of emulsion (6): (1) A mixture of 10% by weight gelatin aqueous solution 100 (1) was dissolved at 55°C, then added to the gelatin aqueous solution (2) previously heated to 55°C, and emulsified in a colloid mill.

Y-1 Layer-10: Blue-sensitive high-sensitivity silver halide emulsion layer/The following changes were made to the silver halide emulsion liquid of i-9.

The silver halide emulsion liquid prepared in this way has a dry film thickness of 2
．． It was applied to a thickness of 5μ.

Layer-11: Gelatin protective layer (dry film thickness 1.2 μm) Table 1 shows the scavengers of oxidized developing agent according to the present invention and the conventional developing agent oxidized product scavengers added to ll-5 in the coated sample thus prepared. Various samples were prepared by adding different amounts.

The sample prepared as described above was exposed to red light for 10 seconds through a continuous wedge, and color development was performed according to the color development process for internal color negatives described above to mix colors from the red-sensitive layer to the green-sensitive layer. The degree of

In addition, the removal efficiency of the scavenger of oxidized developing agent was examined after each of Samples 1 to 25 was stored for 4 weeks and 8 weeks under the conditions of an oxygen partial pressure of 600 mHH, a temperature of 60° C., and a relative humidity of 80%. (Note that storing each sample for 4 weeks and 8 weeks under the above temperature and relative humidity conditions corresponds to storage for about 1 year and about 2 years at room temperature.)
These results are shown in Table-1.

In addition, in common with the following examples, the density of the colored image was measured using a Sakura photoelectric densitometer PDA-60 (manufactured by Konishiroku Photo Industry Co., Ltd.), and the display of Da/Db is the color density of the exposed emulsion layer. (Db) represents the ratio of the density (Da) in which the unexposed emulsion layer develops color due to the diffusion of the oxidized developing agent, and the symbols a and b represent B, G, and R (color sensitivity), respectively. The smaller this value is, the better the removal efficiency of the oxidized herbal drug.

Table-1 Qin Comparison-1 **Hata Comparison-3 Example 2 Samples 26 to 38 were prepared by sequentially coating the following layers on a support made of polyethylene-coated paper from the support side.

Layer-1: Blue-sensitive) Silver halide emulsion layer consisting of silver chloride iodobromide containing 1 mole of silver iodide and 19 moles of silver chloride, containing Schizelatin 4002 per mole of silver halide, and a blue-sensitive sensitizing dye. Yellow turnip 2-(Y-2) sensitized with 2.5 X 10-' mol/mol of silver halide and dissolved and dispersed in dibutyl phthalate at 2 X 10-'' mol per mol of silver halide. The silver halide emulsion liquid contained therein was coated so that the amount of coated silver was 4,001 mm (dry film thickness: 2.0 μm).

Layer-2: Color mixture prevention layer 50 of an emulsion of an oxidized developing agent scavenger (7) was added to a 10% by weight gelatin aqueous solution 500F and coated so that the dry film thickness was 0.8 μm.

Composition of emulsion (7): ■ 10% by weight gelatin aqueous solution 1000? The mixture (1) was dissolved at 55°C, added to the aqueous gelatin solution (2) previously heated to 55°C, and emulsified using a colloid mill.

Layer-3 = green-sensitive silver halide emulsion layer containing silver chlorobromide containing 20 moles of silver chloride, containing 5009 shigelatin per mole of silver halide, and containing 2.5 moles of green-sensitive sensitizing dye per mole of silver halide. The magenta coupler (M-2), which was sensitized using X 10" moles and dissolved and dispersed in tricresyl phosphate, and 4-dioctyloxy 2,5-di-tert-aminobenzene were halogenated. A silver halide emulsion containing 2X10-' mol and 1.2X10-' mol, respectively, per mole of silver,
Coating was carried out so that the coating silver amount was 500 W/d (dry film thickness: 2.2 μm).

Layer-4=color mixing prevention layer Same as layer-2.

Layer-5: Red-sensitive silver halide emulsion layer A silver chlorobromide emulsion containing 20 moles of silver chloride, containing 500 F of gelatin per mole of silver halide, and containing 17 moles of silver halide and red-sensitive sensitizing dye 2. A silver halide emulsion containing 2 X I F" moles of cyan coupler (C-2) sensitized using 5 X 10-1 moles and dissolved and dispersed in tricresyl phosphate. was coated to give a coated silver amount of 500' IF/arm (dry film thickness 2.3 μm).

Layer-6: Protective layer...gelatin layer In this case, each silver halide emulsion used in layer 1, layer 3, and layer 5 was prepared by the method described in Japanese Patent Publication No. 7772/1983, and each was thiolized. Chemically sensitized using sodium sulfate pentahydrate and 4-hydroxy-6 as a stabilizer.
-Methyl-1,3,3a.

It contained 7-chitrazaindene sodium salt, bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid.

-2 -2 Samples 26 to 38 prepared in this manner were added with an oxidized developing agent scavenger as shown in Table 2. These samples were stored for 4 weeks at a temperature of 60°C and a relative humidity of 80% in an atmosphere with an oxygen partial pressure of 600 tsHg (this is equivalent to storage for about 1 year at room temperature).
.

The sample prepared as described above is exposed to green light through a continuous wedge, and color development is performed according to the above-mentioned internal color positive color development process to create a color mixture from the green-sensitive layer to the blue-sensitive layer and red-sensitive layer. The degree was evaluated.

Table 2 As is clear from Tables 1 and 2, oxidized development was observed in samples that did not contain the compound according to the present invention (developing agent oxidized product scavenger) in the layer between two or more types of silver halide emulsion layers. The drug diffuses into the undeveloped silver emulsion layer and reacts with the coupler contained in that layer to form a dye. Using the compounds according to the invention, the proportion of color mixture in each layer was significantly reduced. It is also clear that both the sample immediately after coating and the sample stored for a long period of time are extremely effective in removing oxidized developing agent compared to the comparative compound.

Example 3 On a support made of polyethylene-coated paper, silver chlorobromide containing 20 moles of silver chloride was prepared per mole of silver halide, and gelatin containing 400 f per mole of silver halide was used to increase blue sensitivity. The compound of the present invention (developing agent oxidized product scavenger) sensitized using 2.5 x 10-' mol of a sensitive dye and dissolved and dispersed in dibutyl phthalate was added to 1 mol of silver halide, 2 x 10 Samples 39 to 50 were prepared by coating a silver halide emulsion liquid containing -1 mol so that the amount of silver coated was 400,119. Then, according to the above-mentioned color development process for internal color positives, the process cost for internal color positives was used as color development (5), and color development (
As B), the color developer in the color development step is treated at 36°C.
The color change due to the scavenger of oxidized developing agent was evaluated by changing the time to 2 minutes.

Table 3: No stains occur due to mechanical problems. In particular, it is clear that staining does not occur even when the developing temperature is raised to perform rapid processing.

(f) Specific effects of the invention When the compound according to the invention is incorporated into the photographic constituent layer of a silver halide photographic light-sensitive material, it exhibits an excellent scavenger effect compared to conventional substituted hydroquinones. That is, the compound according to the present invention acts as a scavenger for the oxidized developing agent within the photographic constituent layer, has high scavenging efficiency for the oxidized developing agent, and can maintain the scavenging effect for a long period of time. There is no substantial adverse effect on the development of silver oxide. Furthermore, the compound according to the present invention is not oxidized itself to produce a colored product, nor does it undergo a coupling reaction with an oxidized developing agent to produce a colored product, and is substantially colorless. Because it is a compound, it has extremely excellent properties such as not causing color capri.

Applicant: Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Scope of Claims] A silver halogenide photographic light-sensitive material comprising, on a support, at least one photographic constituent layer containing at least one compound represented by the following general formula CI). General formula CI) [However, one of X and Y is 廿TL>n (where 几 is a halogen atom, an alkyl group, an aryl group, an acyl group, a carboxyl group, an acylamino group, a carbamoyl group, a sulfonyl group, represents an alkylthio group or a sulfonamide group, and n represents an integer from 0 to 5), and the other represents an aryl group. ]