JPS59212837A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To reduce color fog and stains, etc. by incorporating a scavenger superior in effectivity in a photographic constituent layer. CONSTITUTION:At least one of photographic constituent layers contains a non- diffusive colorless compd. represented by formula ( I ) in which R1, R2 are each a univalent org. group, such as straight or branched alkyl, alkenyl, cycloalkyl, aralkyl, or aryl, or a heterocyclic group, such as furanyl, pyridinyl, pyrazinyl, pyrimidyl, quinolinyl, indonyl, and at least one of both is a cycloalkyl or hetrocyclic group.

Description

[Detailed description of the invention] Industrial applications The present invention can be utilized as four technologies.

Further, the present invention relates to a photographic material containing -rogen,
More specifically, the present invention relates to a halogenated photographic material with improved color staining and resultant flashing.

PRIOR TECHNOLOGY In general, silver halide color photographic materials, in particular, are produced by exposing a silver halide color photographic light-sensitive material phase to light and then treating it with a color developing solution containing an aromatic primary amino acid herbal medicine. The method of forming a color image by reacting the acidic form of the developing agent described above with a photographic coupler is well known in the art.

In addition, in such a color image forming method, the above-mentioned aromatic primary amine developing agent is oxidized by air, and this oxidized developing agent reacts with the coupler in the unexposed area of the light-sensitive material to form a dye. When formed, color capri occurs, which is also known as color fog, and is known as an undesirable phenomenon.

In addition, for color light-sensitive materials with a multilayer structure, such as ordinary halogenated button color light-sensitive materials, which are coated with emulsion layers containing couplers with different color sensitivities and different hues, The phenomenon of color mixing can sometimes become a problem. As is well known, in order to obtain a color image with good color reproducibility, it is necessary that at least the coupler contained in the same layer as the exposed silver halide develops color, so the above color mixing phenomenon will never occur. This is not a desirable phenomenon.

In other words, the oxidized aromatic primary amino developing agent generated during the color development process is a low-molecular-weight, and does not remain only within the formed layer but diffuses into adjacent layers, which affects the correspondence between color sensitivity and color development. As a result of this disturbance, the above-mentioned color mixing phenomenon occurs. As a means for preventing the occurrence of the above-mentioned color mixing, air fog, color contamination, etc., a method of using, for example, a hydroquinone yarn compound is conventionally known.

Regarding these hydroquinone compounds, alkylhydroquinones are described in, for example, Japanese Patent Publications Nos. 50-21249, 50-23813, 49-106329, 49-129535, and 55-43521. and U.S. Patent No. 2゜418.613
The specification describes arylhydroquinones. The function of these no-hydroquinone compounds is that they react with the oxidized form of the diffusible developing agent, leading to compounds that can no longer participate in the dye image forming reaction. Also called a scavenger.

The use of these scavengers is described, for example, in U.S. Pat.
No. 2, 7 (No. 14,713, JP-A-55-435)
No. 21, No. 56-83742, No. 56-109344
No. 57-22237, etc.

The basic function of these scavengers is, for example, to add and contain the scavengers in a non-photosensitive intermediate sandwiched between photosensitive and silver halide emulsion layers having different color sensitivities. During the color development process, the scavenger in the intermediate layer converts the oxidized form of the developing agent that has mutually diffused from the emulsion layer into a compound that cannot participate in the dye image forming reaction. This can prevent color mixing.

Therefore, a scavenger having the above-mentioned effects must not migrate from the layer in which it is contained to other layers and cause photographically unfavorable side effects, and must not be one that causes undesirable photographic side effects. When added to emulsion j-,
C must not be present as it will inhibit the developability of the emulsion layer. In addition, during the manufacturing process of the photosensitive material and after the straddling process, crystals must not be precipitated and coloring by-products that may adversely affect the physical properties of the coated material must not be produced. Furthermore, it is required to have properties that are stable over a long period of time, without impairing its effectiveness, and without causing any harmful side reactions.

Although it is preferable for a scavenger to satisfy all of the above-mentioned properties, conventional hydroquinone compounds have some conditions that are desired to be further improved.

Therefore, the main objects of the present invention are as follows. It is something that

OBJECTS OF THE INVENTION The first object of the present invention is to be able to efficiently prevent the occurrence of capri, color contamination, color mixture, etc. without adversely affecting the silver developability, and to provide a long-term The purpose of G2 is to provide a new scavenger that is stable even during storage. The purpose is to provide materials.

Structure of the Invention The present inventors have repeatedly investigated the above-mentioned problems, and the above object is to provide a silver halide photographic light-sensitive material having at least one layer of JC&layer on a support. It has been found that this can be achieved by using a silver halide photographic light-sensitive material in which at least one of the constituent layers contains a non-diffusible and virtually colorless compound represented by the following general formula CI).

General Formula (I) In the formula, R1 and R1 represent a monovalent organic group, and at least one of R1 and R2 represents a cycloalkyl group or a heterocyclic group.

The present invention will be explained in more detail below.

Compounds useful in the present invention are those of the general formula (I
), but in the general formula (I),
The monovalent organic group represented by R1 and R1 includes, for example, a straight-chain alkyl group having 1 to 40 carbon atoms and a branched alkyl group (e.g., methyl group, ethyl group, n-propyl group, inpropyl group, n- Butyl group, tert-butyl group, n-
Pentyl group, n-decyl group, tertfyl group, n-dodecyl group, Free-dodecyl group, tert-dodecyl group, n-pentadecyl group, Bee-pentadecyl group%
tert -pentadecyl f% 8@e-octadecyl group, tsrt-octadecyl group), substituted alkyl group having a total number of carbon atoms of 1 to η [substituents include halogen atoms such as chlorine atom or bromine atom, hydroxy group , an alkoxy group, a substituted amino group (including an alkylsulfamoyl group, an arylsulfamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.), a cyanide group, etc., and specifically t/i4-chlorobutyl group, 2 -hydroxyethyl group, 3-methoxyclopyl h, "n-
Butylsulfamoylpropyl group, etc.], 3 to 3 carbon atoms
Substitution of n yT = t7 company iq ^ Alkenyl group (e.g. allyl 4), substituted or unsubstituted cycloalkyl group having 5 to 12 carbon atoms [Substituents include, for example... rogen atom, hydroxy group, alkoxy group, substituted amino group,
There are unsubstituted amino groups, cyano groups, acyl groups, etc., specifically, for example, cyclopentyl group, cyclohexyl group, cyclooctyl group, 2-aminone chlorohexyl group, 4-t
An ert-butyl 7-chlorohexyl group, a 2-hydroxycyclohexyl group, etc. can be added. ]Number of carbon atoms: 7
~22 substituted or (unsubstituted) aralkyl groups (e.g. benzyl group, huene (12) O) T (13) H (14) (16) 0■ (17) H υh (18) H (19) O ■T (2fJ) (21) (?2) H (o) Next, a typical synthesis example of the compound related to the present invention will be shown.

Synthesis Example 1 (Synthesis of Exemplified Compound (7)) (a) 2-benzyloxy-4-nitroaniline (
Synthesis of Intermediate A) 55% oil dispersion (hydrogenation) 2-amino-5-
36.6 g of nitrophenol was added and stirred at 40°C for 1 hour. Add 41.0% of benzyl bromide to this solution. li+ was added dropwise over the addition period and stirred at 40° C. for 2 hours. After the reaction was completed, the reaction solution was poured into water (21), and the separated solid was filtered and washed with water. This solid was recrystallized from ethanol to obtain 38.6 g of yellow powder (Intermediate A). Melting point 1
43-147°C, [b) N-(2-benzyloxy-5
-nitrophenyl)-cyclohexylsulfonamide (
Synthesis of intermediate B) 250 g of intermediate A obtained by the synthesis of the above (,),
To a solution containing 250 mJK of pyridine, 18 J.9 of cyclohexylsulfonyl chloride was added.

This reaction solution was heated under reflux for 5 hours. The reaction solution was poured into ice water containing 500% of 2N hydrochloric acid. The precipitated solid was filtered and recrystallized from ethanol to produce a brown solid (Intermediate B
) 2'9.6 g was obtained. Melting point: 158-162°C, (C) Synthesis of N-(2-benzyloxy-4-aminophenyl)-cyclohexylsulfonamide (Intermediate C) 20.5 g of Intermediate B obtained by the above synthesis of Tbl
in THF200 containing 1.0g of Raney nickel catalyst.
- and hydrogenation reaction was carried out at room temperature.

After 6 hours, the catalyst was filtered and the clear liquid was distilled off under reduced pressure to obtain a white solid. This solid was recrystallized from acetonitrile to give a white powder (Intermediate C) 19.2. S'
I got it. Melting point 195-199°C, Td) Synthesis of 2-7chlorohexylsulfonamyl'-5-(2-chloro-5-nitro)benzenesulfonamide-benzyloxybenzene (medium solid D) Synthesis of (c) above 16.0y of intermediate C obtained by
2-chloro-5- in a solution of pyridine 100-
Nitrobenzenesulfonyl chloride 10.3Jill
1- was added and heated under reflux for 6 hours. The reaction solution was diluted with 2N-hydrochloric acid 3
Pour into ice water containing 00F. The precipitated solid was recrystallized from acetonitrile to give a yellow solid (Intermediate D) 16.8
I got a 9. Melting point 181-185°C, (e) 2-cyclohexylsulfonamide-5-(
Synthesis of 2-chloro-5-amino)benzenesulfonamidophenol (intermediate E) 12. Synthesis of the intermediate obtained by the synthesis of (d) above. Og
1. THF in Og palladium-carbon catalyst 1
001d and hydrogenation reaction was carried out at room temperature. 3
Time later, catalyst! The clear liquid was distilled off under reduced pressure to obtain a white solid, which was recrystallized from acetonitrile to obtain 10.2 g of Intermediate E. Melting point: 160-165°C, (fl Synthesis of Exemplary Compound (7) 9.5 g of Intermediate E obtained in the synthesis of the above (@) was added to a solution of distilled and dried THF80jiA!, sodium carbon hydrogen 7, OI and 7.2 g of 2-(2,4-di-tert-pentylphenoxy)-butyryl chloride at 40
The reaction was carried out at ℃. After 2 hours, the reaction solution was evaporated to 1/3 under reduced pressure, and then poured into a 300-pH buffer solution. The precipitated brown solid was filtered, this solid was dissolved in a 1:1 solution of ethanol and acetonitrile, and treated with activated carbon.
Recrystallized to white crystals (exemplified compound +7) ] 1
．． 7. Got @.

When the above-mentioned exemplified compound (with a melting point of 170 to 172°C) was subjected to mass spectrometry (FD ionization method), %761 of ions were detected.

(Elemental analysis value) CHN S (J calculated value 59,89 6.83 5.51 8,41
4.66 Analysis value 59.70 6.79 5.61 8
．． 29 4.53 Synthesis Example 2 (Exemplary Compound (Synthesis in 1 Day)) (a) Synthesis of N-(2-benzyloxy-5-nitrophenyl)-4-dodefluoxysulfonamide (Intermediate F) Step of Example 1 (medium m1 body AI2.OI obtained with al
was dissolved in pyridine 8ON, and 4-dodecyloxybenzenesulfonyl chloride was added thereto.

This mixture was heated at R current for 2 hours. After cooling the reaction solution, 2
It was poured into ice water containing 9500 ml of N-dioxide. The precipitated solid was filtered and recrystallized from ethanol to obtain a brown solid (
19.8 g of intermediate F) was obtained. Melting point 90-95°C, (b) Synthesis of 2-(4-dodecyloxy)-phenylsulfonamido-5-aminephenol (intermediate G) Intermediate F synthesized from (b) K above 4. OI
! in THFl containing 1.0 g of palladium-carbon catalyst.
oo- and hydrogenated. After 3 hours, the hydrogen phase did not decrease, so the catalyst was filtered and the clear liquid was distilled off under reduced pressure to obtain a white substance. This solid was recrystallized from acetonitrile to give a white powder (Intermediate G)
I got o, oy.

(C) Synthesis of Exemplary Compound (18) After adding 8-quinolinesulfonyl chloride 2,6I to a solution of intermediate G 9.0 , j7 synthesized in (b) above dissolved in pyridi750-, 5 hours were added. The mixture was heated to reflux.

After cooling the reaction solution, it was poured into ice water containing 200 ml of 2N hydrochloric acid. The precipitated solid was dissolved in acetonate (IJ) and treated with activated carbon, then recrystallized to give white crystals (Exemplary Compound 18).
7.6g was obtained. When mass spectrometry (FD ionization method) was performed on the above exemplary compound (18) having a melting point of 188 to 192°C, a parent ion of m/e 639 was detected.

(Elemental analysis (if) CHN S Calculated value 61.95 6,45 6.57 10.02
Analysis value 61.99 6.46 6.54 10.10
The compound according to the present invention obtained by the above synthesis method is a scavenger that is used in photosensitive materials to effectively prevent color staining, color mixing, etc., and has particularly excellent stability during long-term storage. is preferably added to the non-photosensitive hydrophilic colloid layer of the photographic constituent layers constituting the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the light-sensitive material of the present invention).

The above-mentioned non-photosensitive hydrophilic colloid layer, such as an intermediate layer,
It means a filter layer, a protective layer, a color mixture prevention layer, etc.

In a preferred embodiment of the present invention, the compound according to the present invention is contained in a non-photosensitive hydrophilic colloid layer, which is an intermediate layer interposed between a plurality of photosensitive silver halide emulsion layers. It may be added to the above emulsion layer. When the compound according to the present invention is added to the intermediate layer, the amount used is 200 to 200.
The coating amount is preferably 0.0 cm/cm, and when added to a silver halide emulsion layer, the amount of addition is preferably about 3.times.10 to 5.times.10 moles per mole of silver halide.

In order to incorporate the compound according to the present invention into the above-mentioned photographic constituent layers, known methods such as U.S. Pat. No. 2,322
．． The method described in No. 027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (triphenyl phosphonate, tricresyl phosphate, dioctyl butyl phosphate, etc.), citric acid esters (acetyl tributyl citrate, etc.), benzoic acid ester(
octyl benzoate, etc.), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dinotoxyethyl succinate, dioctyl azelate), trimesine esters (e.g. tributyl trimesate), etc., or with a boiling point of about 30°C to 150°C. After being dissolved in an organic solvent such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, .beta.-ethoxyethyl acetate, methyl cellosolve acetate, etc. at .degree. C., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic heating medium may be mixed and used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used.

Gelatin is mainly used as the hydrophilic colloid in the non-photosensitive hydrophilic colloid layer to which the compound according to the present invention is preferably added. The gelatin used in the present invention is
Any gelatin may be used, such as so-called alkali-treated gelatin acid-treated gelatin or enzyme-treated gelatin. It is also possible to use partially hydrolyzed low molecular weight gelatin. Further examples include derivative gelatin such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein, or alginic acid, synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone, and cellulose conductors such as carboxymethyl cellulose. , these can be used independently or in combination.

In the present invention, the non-photosensitive hydrophilic colloid layer may contain a hardening agent, an interfacial fδ property agent, a polymer latex,
It can contain matting agents, plasticizers, belts, inhibitors, various dyes, ultraviolet absorbers, anti-fading agents, and the like.

Among these, hardening agents that can be preferably used in the present invention include formaldehyde, glyoxal, dimethylol urea, 2,3-dihydroxydioxane, bis(vinylsulfonyl) methyl ether, and 2,4-
Examples include trichrome-6-hydroxy-S-toIJ azine and mucochloric acid.

In the present invention, preferred surfactants include saponin, alkylene oxide, nonionic surfactants such as glycerin, cationic surfactants, anionic surfactants, amphoteric surfactants, etc. .

In the present invention, the silver halide of the photosensitive emulsion of the photosensitive silver halide emulsion layer is a conventional halogenated silver halide such as silver bromide, silver chloride, silver iodobromide, silver chloroiodobromide, etc. Anything used in silver photographic emulsions is included.

The silver halogenide emulsion used in the light-sensitive material of the present invention is
Various manufacturing methods including the conventional manufacturing method, such as the method described in Japanese Patent Publication No. 46-7772, or the method described in U.S. Patent No. 2,592.250, are used. So-called conversion emulsions, such as forming an emulsion of silver salt grains that are larger than silver oxide and consisting of at least a portion of silver salt, and then converting at least a portion of these grains into silver bromide salt or silver iodobromide lumps. It can be produced by any manufacturing method such as the manufacturing method of 2003 or the so-called Lippmann emulsion manufacturing method. This silver halide emulsion contains chemical sensitizers such as thiosulfate, allylthiocarbamide,
Sulfur sensitizers such as thiourea, allylisothionanate, cystine, etc., inactive selenium sensitizers, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, 2-aurothiapenzthiazole methyl chloride, etc. Gold compounds such as ammonium chloride, palladium compounds such as sodium chlorovaladite, platinum compounds such as potassium chlorooleate, noble metal compounds such as ruthenium compounds, rhodium compounds, iridium compounds, etc. Sensitization can be achieved using a sensitizer or a combination of such sensitizers. In addition to chemical sensitization, this emulsion can also be reduced sensitized using a reducing agent, such as triazoles, imidazoles, azaindenes, benzthiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof. It can also be stabilized with a thioether W, a 4M ammonium salt type compound, or a polyalkylene oxide type sensitizing compound.

In the light-sensitive material of the present invention, glycerin, 1,5-
Wetting agents such as dihydroxy alkanes such as bentanediol, esters of ethylene bistallicholic acid, hisethyl diethylene glycol succinate, water-dispersible fine particulate polymer compounds obtained by emulsion polymerization, star-forming agents, film property improvers, etc. It can be included. Further, the silver halide emulsion layer may contain a hardening agent of the same kind as that added to the non-photosensitive aqueous colloid layer.

The blue-sensitive emulsion, green-sensitive emulsion 2, and red-sensitive emulsion used in the uninvented light-sensitive material are optically sensitized using appropriate sensitizing dyes in order to impart photosensitivity to the desired V-long range, respectively. Ru. Various sensitizing dyes can be used. Each of these sensitizing dyes may be used alone or in combination of two or more.

Examples of the sensitizing dyes advantageously used in the present invention include the following. That is, as sensitizing dyes used in blue-sensitive emulsions, for example, U.S. Pat.
1, British Patent No. 424.559, British Patent No. 2,161,
Examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes described in No. 1, No. 331, etc. In addition, as sensitizing dyes used in green-sensitive emulsions, for example, U.S. Pat.
No. 08, No. 2.739.149, No. 2.945,
Examples include 7-anine dyes, merocyanine dyes, and complex cyanine dyes described in No. 763, British Patent No. 505,979, and the like. Furthermore, sensitizing dyes used in red-sensitive emulsions include, for example, U.S. Pat. No. 2,269.
No. 234, No. 2.270,378, No. 2.442
, No. 710, No. 2,454,629, No. 2.77
Examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes described in No. 6.280.

Next, as couplers that can be used in the light-sensitive material of the present invention, there are known 2-equivalent or 4-equivalent couplers, and for yellow couplers, open-chain acylacetamide couplers such as pino(lylacedoanilides, benzoylacetanilides), etc. etc., and as a magenta coupler,
Examples include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, indashilon couplers, and the like.Cyan couplers include naphthol couplers and phenol couplers. Preferably, these couplers are non-diffusible couplers that have a hydrophobic group called a ballast group in their molecules.In addition, colored couplers that have a color correction effect, or development inhibitors that are used during development. Coupler (L) which emits IR coupler (also called IR coupler) can also be used. It is also possible to use a colorless DIR compound in which the product of the coupling reaction is colorless and releases a development inhibitor.

Such couplers are generally present in amounts ranging from 2 x 10 to 2 moles, preferably [7 or 1 x 10
It is added about 5×10 mole/l/l to 5×10 mole.

As a method for impregnating a coupler into a silver halide emulsion layer, the above-mentioned known method is used, ie, U.S. Pat. No. 2,322
．． The method described in No. 027 can be used 1
However, when the coupler has an acid group such as carboxylic acid sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The layer structure of the light-sensitive material of the present invention is preferably the same as the color light-sensitive material used for color reproduction by the usual subtractive color method, but it does not necessarily have to be the same.・Specifically, a blue-sensitive photosensitive layer containing a yellow coupler for forming a yellow dye image, a green-sensitive photosensitive layer containing a magenta color for forming a magenta dye image, and a cyan photosensitive layer containing a yellow coupler. Basically, the structure consists of three layers: a red-sensitive photosensitive layer containing a cyan coupler for forming a dye image, and one or all of these layers have two layers with different sensitivities. Alternatively, the photosensitive material of the present invention may have three layers in addition to these basic photosensitive layers to improve photographic properties such as coloring characteristics, color reproducibility, and granularity of coloring dyes. A protective layer is provided as the top layer, an intermediate layer and a filter layer are provided between the layers, and a non-photosensitive hydrophilic colloid layer such as an undercoat layer and an antihalation layer is provided as the bottom layer. We aim to strengthen the material, prevent color staining, improve graininess, improve color reproducibility, and improve film adhesion.

Examples of the support in the light-sensitive material of the present invention include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, and polyolefin films such as polyethylene.

There are polystyrene films, polyamide films, polycarbonate films, baryta paper, polyolefin paper, polypropylene synthetic paper, glass plates, metals, etc., and these supports are selected as appropriate depending on the intended use of the IL photosensitive material. be done.

The first color developing agent used in processing the photosensitive material of the present invention has a pH of 8 or more, preferably a pH of 9 to 9.
12 alkaline aqueous solution. The aromatic primary amino developing agent used as the developing agent is a compound having seven primary amide groups on the aromatic ring and has the ability to develop phosphorized silver halide. refers to a precursor that forms a chemical compound.

The above-mentioned developing agent is typically p-phenylenediamine type, and the following are preferred examples.

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-methoxyethylaniline, 3-β-methanesulfonamidoethyl-
4-amino-1i, N-diethylaniline, 3-methquin-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-β-methoxyethylaniline, 3 -acetamide-
4-amino-N, N-diethylaniline, 4-amino-
N, N-dimethylaniline, N-ethyl-N-β-[β
-(β-methoxyethoxyethoxyethoxy)ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β
-methoxyethoxy)ethyl-3-methyl-4-aminoaniline and salts thereof, such as sulfate, salt salt, sulfite, p-1 luenesulfonate, and the like.

In addition, these color developing solutions may contain various additives, such as alkaline agents, buffering agents, and buffering agents, as necessary.
Development accelerators, anti-capri agents, preservatives, etc. are added.

After imagewise exposure of the photosensitive material of the present invention and color development processing, bleaching processing can be carried out by a conventional method.

This process may be done simultaneously with the footwear or separately. This processing solution can also be used as a bleach-fixing bath by adding a binder if necessary. Various compounds can be used as bleaching agents, and various additives, including marking promoters, can also be added.

The effects of the present invention can be exhibited in various forms of silver halide photosensitive materials. A photosensitive material having a silver halide emulsion layer containing a diffusion-resistant coupler on the one-layer support is processed with an alkaline developer containing an aromatic primary amine color developer to make it water-insoluble or highly diffusible. The purpose is to leave the colored ligatures in the emulsion layer.

In another form, a light-sensitive material in which a silver halide emulsion layer combined with a diffusion-resistant coupler is formed on a support is processed with an alkaline monopropylene developer containing the above-mentioned color developing agent to form an aqueous medium. All kinds of silver halide colors, such as so-called diffusion transfer type films, color positive films, color reversal films, and color papers, which produce soluble and diffusible dyes and transfer them to an image-receiving layer made of other hydrophilic colloids. Includes photographic materials.

Typical processing steps and processing solutions applied to the photosensitive material of the present invention include, for example, the color development processing method for color negatives described in JP-A-57-109950, and furthermore, JP-A-57-96339. The color development processing method for color positives described in , etc. can be widely applied.

The present invention will be explained in more detail with reference to examples below, but the present invention is not limited thereto.

Example 1 On a cellulose acetate film support having a 'F coating layer, layers having the following composition were sequentially coated from the support side to prepare a sample.

Layer-1: Ration prevention layer Layer in which black colloidal silver is dispersed in gelatin colloid Layer-2 Gelatin intermediate layer (dry film thickness 10 μm) L So-3 Red-sensitive low-sensitivity emulsion layer 6 mol% silver iodide Containing iodobromide limestone (average particle size 0.3
μ, 1 kg of emulsion (silver halide HIO, @, containing 70.9 g of gelatin) is prepared by a conventional method, for example, in Japanese Patent Publication No. 46-7.
It was prepared by the method described in No. 772. 1kg of this emulsion
To this was added 210 ml of a 0.1% methanol solution of the following ingredients as a sensitizing dye, and 4-hydroxy-6-methyl-1,3,3a as a stabilizer.

2 TJ vri of a 5% aqueous solution of 7-chitrazaindene and the following emulsion (2) were added.

(Sensitizing dye) [Emulsion (1)] (A) 10% (heavy 'JiL') Seratin aqueous solution
1000 fI\ethyl acetate 10
〇-Preparation method...composition? ! After dissolving I(B) at 55°C,
In addition to composition (A) preheated to 55°C, colloid °
Emulsify in a mill.

(C-1) H 1 [Emulsion (2)] (A) 10% by weight gelatin aqueous solution x000J9
Preparation method: the above emulsion (same as method 11).

(CC-1) Next, after adding emulsion (2), a 2% methanol bath solution of bis(vinylsulfonylmethyl)ether was added as a gelatin hardening agent, and red-sensitive, low-sensitivity silver halide was added. An emulsion liquid was prepared, and this emulsion was coated to a dry film thickness of 3.0 μm.

Layer-4 Red-sensitive high-sensitivity emulsion layer An emulsion having the same composition as in Layer-3 except for the following changes was coated to a dry film thickness of 2.4 .mu.m.

That is, the average particle diameter of the rogensed steel particles is 1.0μ,
The amount of added sensitizing dye was 1501d, the emulsion (11 to 32
0g, and emulsion (2) was 30g.

Layer-5 Color mixing prevention layer 1000 g of a 4#% gelatin aqueous solution was mixed with 19% of the following emulsion (3) containing an oxidized developing agent scavenger.
0.9 was added to give a dry film thickness of 0.8 μm.

[Emulsion (3)] (A) Tow gelatin aqueous solution 1oo
o! Preparation method I: Same as the method for emulsion (1) above.

Layer-6 Green Sensitive Emulsion Layer To 1 part of the silver iodobromide emulsion used in jti-3 above, 220 m of a 0.11% aqueous solution of the following sensitizing dye was added.
320g of magenta coupler emulsion (4) with the following formulation.
Furthermore, 50 g of the following emulsion (5) was added.

[Emulsion (4)] (A) 103 (fish% gelatin water bath fi 1
000g preparation method: Same as the method for emulsion (1) above.

(M-1) l (CM-1) c.

[Emulsion (5)] (A) 1 (3% by weight gelatin water soluble fi 1
o009 Preparation method: Same as the method for emulsion (1) above.

Next, a bis(vinylsulfonylmethyl d was added to form a green-sensitive, low-sensitivity silver chloride emulsion) solution was prepared as a gelatin film agent.This emulsion was coated to a dry film thickness of 3.0 μm.

Iso-7 Green-sensitive emulsion layer Jso-6 An emulsion having the same composition as in Jso-6 except for the following changes was coated to a dry film thickness of 2.5μ. The average particle size of silver oxide grains was 1.0 μ, the legal content of silver halide was 6.5 mol%, the amount of sensitizing dye added was 100 Tnl, the emulsion was 150 g, and the emulsion (5) was 1009 And so.

Layer-8 Yellow colloidal silver layer (dry film thickness 1.4μ) #
-9 f-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion 1, the same as that used in layer-3, was mixed with a 0.1 Keiyo% aqueous solution of the following sensitizing dye 180+1! and 1,400 yen-4 coupler emulsion (6) according to the following formulation.
9 added.

(Sensitizing dye) [Emulsion (6)] (A) 10 weight 1% gelatin water soluble 7I! 1
0009iMj# method: Same method as the emulsion (1).

(Y-1) Next, 51 J Tjl of a 2% by weight aqueous solution of bis(vinylsulfonylmethyl)ether was added as a gelate hardening agent to prepare a low-back sensitivity halide emulsion.

This emulsion was coated to a dry film thickness of 3.0 μm.

Layer - 10'% i' Sensitivity 11 - Sensitivity Emulsion Layer An emulsion having the same composition as the halogenated emulsion composition of Layer-9 except for the following changes was coated to a dry powder thickness of 2.5 μm. I did it.

That is, the average grain size of silver halogenide grains is 1.2μ,
The amount of sensitizing dye added was 80 rnl, and the amount of emulsion (6) was 50 rnl.
It was set to 0.9.

Layer-11 Gelatin protective layer (dry film thickness 1.2μ) □Layer-5 of the coating sample thus obtained contained scavengers as shown in Table 1 below in accordance with the amounts added in Table 1. Samples 1 to 20 were produced.

Using a continuous wedge for each of the above samples, '/1
The results are shown in Table 1. Exposure was carried out for 0.00 seconds, and color development for color negatives was carried out according to the processing steps described below.

Processing process (38℃) Processing time 1iJ] Color development...3 minutes 15 seconds Prefecture White...
・・・・・・6 First second wash・・・・・・・・・・3
Minute 15 Abstract Watch・・・・・・・・・6 minutes 30 seconds Wednesday
Washing... 3 minutes 15 seconds stabilization...
...1 participle second The composition of the treatment liquid used in each granulation step is as follows.

Color developing solution composition: Target solution composition: Foot coating solution composition: Stabilizing solution composition: At the same time, a portion of each sample was heated at 60°C in a pure acidic atmosphere.
, relative humidity [80%] for 4 weeks and 8 weeks. Each of the samples stored in this way was exposed to light and developed in the same manner as described above, and the obtained Table 1 Comparative Compound (]) Comparative Compound (2) As is clear from the results in the above table, 11 of the present invention When a scavenger compound related to the above is added to the intermediate layer 0+η-5 (color mixing prevention layer) interposed between the red-sensitive emulsion layer ν and the green-sensitive emulsion layer, it can be stored for a long time as well as immediately after coating. It can also be seen that the effect of preventing the red-sensitive layer and the green-sensitive layer against color blurring is remarkable compared to the comparative compound even after the comparison, and is superior to that of the comparative compound.

On the other hand, since the comparative compound loses its effectiveness upon storage, the compound according to the present invention has long J4. It was also revealed that they will meet at LJ Mamesada.

Example 2 The following constituent layers were applied from the support side to the J1 layer on a paper support having a polyethylene board, and sample 21-307i-
Created.

Layer-I Night-sensitive emulsion: Silver iodide containing 1 mol % of silver iodide, 19 mol % of silver chloride, 400 g of gelatin per mol of silver halide, and 2.5 x 10 mol of silver chloride. A silver halide emulsion containing a yellow coupler (Y-2) shown below, which is optically sensitized by containing a dye, and which is dissolved and dispersed in dibutyl phthalate, in an amount of 2 x 10-1 mol per mol of silver halide, is prepared. It was applied so that the coating amount was 400+1/g. (Dry film thickness 2.θμ) (Sensitizing dye (Y-2) Layer 2 Color mixing prevention layer 10% gelatin aqueous solution 1000.9% Emulsion enriched with a scavenger of the developer main oxidant (71 2 (1
(117JO was applied so that the dry film Jf, iZ was 0.8μ.

[Emulsion (7)] (A) 'zo heavy lid % gelatin aqueous solution 1 (1
00g preparation method...emulsification of Example 1? 1 (method 11 and +tIj.

Layer-3 green-sensitive emulsion layer contains silver chlorobromide containing mol % of silver chloride, 500.9 mol of gelatin per mol of silver halide, and 2.581 O mol per mol of silver halide in the awn layer. The following magenta coupler (M-2) and 1.4-
Dioctyloxy-2.5-di-tert-amylbenzene as silver halide.

Per mole, respectively -1'L2X10 mole a and 1
．． A halogen emulsion containing 2Xl (J mol) was coated to give a coated silver amount of 500 to 1/1. (Dry film thickness 2
82μ) (sensitizing dye) (M-29 l J So-4 Color mixing prevention layer I Same layer as So-2 - 5 Red-sensitive milky layer A layer with silver chlorobromide containing 9 mol% silver chloride) silver chloride 1
2×10 6 mol of gelatin containing 500 I/mol of gelatin and optically sensitized using the following sensitizing dye at 2.5 The following cyan coupler (C
-2) Apply a silver halide emulsion solution containing 50
It was coated so that it was 0 to /m'. (Dry film thickness 2.3μ
) I C, H, (CH,)4So," (C-2) H Layer-6 Gelatin protective layer (The silver halide agent used in the above layers-1, layer-3 and 7m-5 is , prepared by the method described in Japanese Patent Publication No. 46-7772, and sensitized using sodium thio and carbonate pentahydrate, respectively, and 4-4 as a stabilizer.
Hydroxy-6-methy/L'-1°3.3a, 7-titrazaindene sodium salt, bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid were included.

Samples 21 to 31JK obtained in this way are shown in the second section below.
Scavenger compounds as indicated in the table were added. A portion of each sample was simultaneously stored in a pure oxygen atmosphere at 60° C. and 80% relative humidity for 4 weeks.

Each sample was exposed to green light using a continuous wedge and subjected to color positive color development according to the following process steps, and the results are shown in Table 2 below.

Processing process (30'C) Processing time color development!
・・・・・・3 participle second, Mengbai fixation・・・・・・・
-Washing with water for 1 minute and 30 seconds...2 minutes stabilization...1 minute The composition of the treatment liquid used in each treatment step is as follows.

Color developing solution composition: Bleaching foot solution composition Bistable bath composition: Table 2 From the results shown in the above table, the scavenger compound according to the present invention was added between the evening-sensitive layer and the green-sensitive layer, as well as between the edge-sensitive layer and the red-sensitive layer. When it is contained in the middle layer (color mixing prevention layer) between the back and green sensitive layers, it is possible to prevent the gap between the back sensitive layer and the green sensitive layer, not only immediately after application but also after being stored for 4 weeks under the above storage conditions. It can be seen that the color mixture occurring between the green-sensitive layer and the red-sensitive layer is significantly prevented and improved.

On the other hand, when the comparative compound was used, it became clear that although color mixing could be prevented by coating, this effect was lost after the first 4 weeks of storage.

Example 3 On a paper support having a polyethylene board, silver chlorobromide containing 9 mol % silver chloride, halogenated 14 (more than 1 mol) containing 400 fl of gelatin, and the following sensitized color mixture were halogenated. The scavenger compounds according to the present invention, as listed in Table 3 below, were sensitized using 2.5Xl (J moles per mole of silver) and dispersed in dibutyl phthalate. 2×10 7′ per mole
Sample No. 31 was prepared by applying a silver halide emulsion solution containing silver to a coating weight of 400 to 400/g.

A portion of the above sample was stored for 4 weeks at 60° C. and 80% relative humidity under the same pure atmosphere.

Using a continuous wedge on each sample obtained in this way,
White light exposure lB・1.・Color・− used in Example 2
The film was developed using a color development method for bonding, and the results obtained are shown in Table 3 above. - j (sensitized color accumulation) Table 3 The results in the above table indicate that the samples containing the scavenger compound according to the present invention in the silver halide emulsion layer were not stored under the above-mentioned storage conditions immediately after coating. It was also revealed that no occurrence of minimum concentration increase, ie, staining, was observed even after storage for 4 weeks.

Effects of the invention The scavenger compound according to the invention prevents color mixing.
Not only does it support young fruits, but it is also stable for long-term storage without losing its effectiveness, and does not produce stains.

Agent Sakae IJA Taneshi

Claims (1)

[Scope of Claims] In a halogenated photosensitive material having at least one photographic constituent layer on a support, at least one rti of the photographic constituent layer has a non-diffusing property represented by the following general formula (1). What is claimed is: 1. A silver halide photosensitive material containing a substantially colorless compound. General formula (I) H [wherein R8 and R2 represent a monovalent organic group, R+
OJ: At least one of R2 and R2 represents a Schiff tetraalkyl group or a heterocyclic group. ]