JPS61286853A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To stabilize a dye image against heat and light by incorporating a specified compound in a photosensitive material. CONSTITUTION:The photosensitive material contains a compound having at least one of the hydroxyl groups of a hydroquinone derivatives etherified, and having a group represented by the formula shown on the right in which X is halogen, alkyl, aryl, heterocyclic, hydroxy, alkoxy, nitro, or carboxy,or the like, l is an integer of 0-4, and m is 1 or 2. As a result, yellow staining due to light, heat, and humidity at nonexposed areas can be prevented.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide color photographic material (hereinafter referred to as a color photographic material).
The present invention relates to a color photographic material in which a dye image is stable against heat and light and yellow staining (hereinafter referred to as Y-stain) in non-color developing areas is prevented from occurring.

[Background of the Invention] Color photographic materials are generally obtained by coating a silver halide emulsion in which a coupler is dispersed on a suitable support. Typically, this involves dispersing couplers that couple with the oxidation products of a color developing agent to produce cyan, magenta, and yellow colors in red-, green-, and blue-sensitive silver halide emulsions, respectively. It is manufactured by applying multiple layers in an appropriate order.

After the color photographic material thus obtained is exposed, a final color image is formed through a series of processing steps such as color development, bleaching, fixing, and stabilization.

Color photographic images obtained in this way are stored or exhibited for a long time as records, but these photographic images are not necessarily stable against light or moist heat, and may be exposed to light for long periods of time or When stored under high temperature and high humidity, it is common for dye images to fade or discolor, and furthermore, Y-stain occurs in non-colored areas, causing discoloration of the white background and deterioration of image quality.

Such fading or discoloration of images is a drawback that can be said to be fatal to recording materials.

Compounds that have been conventionally used to eliminate these drawbacks include, for example, 2,5-tert-
Hydroquinone derivatives including butylhydroquinone, 2.6-tert-butyl-p-cresol,
Phenol compounds such as 4.4′-methylenebis(2,6-tert-butylphenol), 2°2′-methylenebis(4-ethyl-5-tert-butylphenol), 4.4′-isopropylidenediphenol, Tocopherol and p-alkoxyphenol compounds are known. Among these, hydroquinone derivatives are particularly well known in U.S. Patent No. 2,360.290J! , same 2.
No. 418.613, No. 2,675,314, No. 2
, No. 701, 197, No. 2, No. 704, 713, No. 2
, No. 728,659, No. 2,732,300, No. 2
, No. 735,765, No. 2,710,801, No. 2,
816,028, British Patent No. 1,363,921;
It is described in Japanese Patent Publication No. 56-40819.

On the other hand, hydroquinone derivatives are also used as color capri (also called color stain) inhibitors. Examples include Shuin Patent Nos. 2,728,659 and 3.700.453.
No., West German Patent Publication No. 2,149,7894, U.S. Patent No. 2.
No. 728,659, No. 2,732,300 (corresponding British Patent No. 752.147), British Patent No. 752.148,
No. 1,086,208', Special Publication 1986-2
No. 1249, No. 513-40818, No. 56-408
No. 16, No. 55-69141, etc.

These compounds are not very effective in preventing fading or discoloration of dye images, or even if they are effective in preventing fading, they cannot prevent the occurrence of Y-stain, or they may cause fogging, poor dispersion, or It may form crystals, making it unsuitable as a dye image stabilizer that exhibits comprehensively excellent effects for photography.

[Object of the Invention] A first object of the present invention is to provide a silver halide photographic material which has excellent color reproducibility and which has significantly improved light fastness of magenta dye images.

A second object of the present invention is to provide a silver halide photographic material having a magenta dye image with little discoloration due to light.

A third object of the present invention is to provide a silver halide photographic material which is prevented from generating Y-stain in uncolored areas due to light, heat and humidity.

[Structure of the Invention] The above object of the present invention is to obtain a hydroquinone compound having a group represented by the following general formula [I] and/or a hydroxyl group of a hydroquinone compound having a group represented by the following general formula [I]. This was achieved using a silver halide color photographic light-sensitive material containing at least one etherified compound (hereinafter referred to as the compound according to the present invention).

General formula [I] [wherein, X is a halogen atom, an alkyl group, an aryl group,
Heterocyclic group, hydroxy group, alkoxy group, aryloxy group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonyl group, alkoxycarbonylamino group, sulfonyl group, alkylthio group, cyano group, nitro group or represents a carboxyl group, l represents an integer of O to 4, and the amount is 1
Represents an integer between ~2. ] [Specific structure of the invention] In the present invention, the group represented by the general formula [I] is bonded via L to a hydroquinone compound or a compound in which at least one of the droxy groups of the hydroquinone compound is etherified. The following general formula [I[], [I[[]
Or, a compound represented by [IV] is formed.

In the above formula, L represents a simple bond or a divalent linking group. xll and steel are x,! described in general formula [I]. and-
It is the same as defined in .

R represents an alkyl group, a cycloalkyl group or an aryl group. R1 and R3 each represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or. Here, L, XSf and l are of the general formula [
I].

In the general formulas [I] to [rV], X represents the group as described above, and examples of the halogen atom represented by X include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Also, examples of alkyl groups include:
Examples of aryl groups include methyl group, trifluoromethyl group, t-butyl group, isopropyl group, t-octyl group, 2-ethoxyethyl group, etc., phenyl group, 2-chlorophenyl group, 4-cyanophenyl group, etc. Examples of the ring group include 2-furyl group, 2-benzothiazolyl group,
Examples of alkoxy groups such as 2-pyridyl group and 2-oxasilyl group include methoxy group, propyloxy group, isobutyloxy group, dodecyloxy group, and aryloxy groups such as phenoxy group, 4-chlorophenoxy group, and 2- Examples of acylamino groups such as naphthyloxy groups include acetamido groups, benzamide groups, hexanamide groups, 3-chlorobenzamide groups, α-(2゜4-di-t-amylphenoxy)acetamide groups, and sulfonamide groups. , such as methanesulfonamide group, butanesulfonamide group, benzenesulfonamide! , 4-
Carbamoyl groups such as t-luenesulfonamide group and dodecanesulfonamide group include, for example, N-butylcarbamoyl group, N,N-diethylcarbamoyl group, N-
Examples of sulfamoyl groups include acetyl-N-octylcarbamoyl group, 3-phenoxypropylcarbamoyl group, etc., such as N-butylsulfamoyl group, NeN-dipropylsulfamoyl group, N-octadecylsulfamoyl group, etc. Examples of the group include phenylureido group, ethylureido group, p-cyanophenylureido group 1, and dodecylureido group. Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, dodecyloxycarbonyl group, and alkoxycarbonylamino group. Examples of the group include methoxycarbonylamino group, ethoxycarbonylamino group, dodecyloxycarbonylamino group, etc.; examples of the sulfonyl group include methanesulfonyl group, propanesulfonyl group, benzenesulfonyl group, 4-cyanobenzenesulfonyl group,
Examples of the alkylthio group such as hexadecanesulfonyl group include ethylthio group, octylthio group, and tetradecylthio group.

Further, as mentioned above, L represents a simple bond or a divalent linking group, but preferably represents the dimension L1-uniform [set-L2+-1,000 L3→T, where n, o and p are each 0 represents an integer of ~2, and Ll represents a divalent linking group selected from the following groups.

Hereinafter, Ll represents a divalent linking group selected from the groups shown below.

R'R'
U or -8Ox -N- R' L3 represents a divalent linking group selected from the groups shown below.

R' Hereinafter, all white In the divalent linking group represented by L+, L2 and L3, R' and Rn are a hydrogen atom, 1 to 1, respectively.
represents an alkyl group having 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X' represents the same group as defined above for X, and Y represents 10- or -8
-, QI represents -C- or -802-, β represents 0 to 4, "represents an integer of O or 1, and S represents an integer of 0 to 10.

The alkyl group represented by R preferably has 1 to 2 carbon atoms.
0 alkyl group, and this alkyl group can have a substituent. Examples of alkyl groups include methyl group,
Examples include t-butyl group, [-octyl group, dodecyl group, octadecyl group, benzyl group, and phenethyl group.

Examples of the cycloalkyl group represented by R include a cyclopentyl group and a cyclohexyl group.

The aryl group represented by R may have a substituent, and examples of the aryl group include phenyl group, 4-methoxyphenyl group, and 2-chlorophenyl group.

The compound according to the present invention is preferably represented by the following general formulas [Vl and [1].

General formula [Vl] General formula [W] In the following blank formula, R1, R2, R3, R' and X have the same meanings as defined in the above general formulas [I] to [TV], respectively.

R1, R2 and R3 are hydrogen atoms, alkyl groups, cycloalkyl groups, aryl groups, alkoxy groups and the like.

X is preferably a hydrogen atom.

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

Below is kinpaku Next, a method for synthesizing the compound according to the present invention will be described below.

(Synthesis of A-14) Bis-(3-chloro-4-hydroxyphenyl) sulfone obtained by basicizing bis-(4-hydroxyphenyl) sulfone with sulfuryl chloride was synthesized using Red Stamp Patent No. 3,894,8.
No. 75, No. 3,933,501, Special Publication No. 51-539
3-chloro0-4-hydroxyphenyl-4'-benzyloxy-31-di-O-lophenylsulfone was obtained by the same method as described in No.
Methyl 2-bromododecanoate was reacted with anhydrous potassium carbonate catalyst in acetone according to the method described in No.
- [4(4-penzylram-dissolved in methanol solution, hydrolyzed the ester, converted to 2-[4-(4-benzyloxyphenylsulfonyl)phenoxy]dodecanoic acid, dried, and dissolved in perthionyl salt) 50℃～60℃
After the reaction was completed, excess perthionyl salt was removed under reduced pressure to obtain 2-[4-(4-benzyloxyphenylsulfonyl)phenoxy]dodecanoic acid chloride.

Next, excess pyridine was added as a deoxidizing agent to a solution of 2.5-di-t-octyloxyaniline in tetrahydrofuran, and after the above acid chloride was added, the solution was heated and stirred at 30°C to 40°C. After the reaction, the mixture was poured into solid ice water to obtain a powder, which was mixed with acetonitrile.
Crystallization was performed from ethyl acetate to obtain the target compound A-14.

The intermediate 2,5-di-n-octyloxyaniline used in the intermediate reaction was synthesized by the following method.

After dissolving 1 mole of hydroquinone in dimethylformamide, a slight excess of potassium butoxide (2,4
2 moles of t-octyl bromide were added, and the mixture was stirred at room temperature for 30 minutes to 1 hour. After the reaction, the reaction solution was poured into ice water, and the precipitated white crystals were collected by filtration, dissolved in glacial acetic acid, and a calculated amount of nitric acid was added dropwise at 0 to 10°C. After the dropwise addition was completed, the mixture was heated to 50°C and stirred for 30 minutes. After the reaction, the reaction solution was poured into ice water, the precipitated yellow crystals were collected by filtration, and 2.5-di-t
-Octyloxynitrobenzene was obtained. Another 2.5
2.5-di-t-octyloxyaniline was obtained by dissolving -di-t-octyloxynitrobenzene in methanol and blowing hydrogen into the solution using palladium carbon as a catalyst.

The compounds of the present invention can be used to form a dye image by oxidative coupling between an aromatic primary amine developing agent (for example, a phenylene diamine derivative or an aminophenol derivative) and a dye-forming coupler in a color development process. It is extremely effective in preventing fog in silver oxide color photographic materials, preventing fading and discoloration of dye images, and preventing Y-stain occurrence.

Examples of dye image-forming couplers used in this type of color photographic light-sensitive material include magenta couplers such as 5-virazoroshika 1 color, pyrazolobenzimidazole couplers, cyanoacetylcoumaron couplers, open-chain azilacetonitrile couplers, and pyrazolotriazole couplers. Examples of yellow couplers include acylacetamide couplers (eg, benzoylacetanilides and pivaloylacetanilides), and examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably used because they can be made non-diffusive by introducing a hydrophobic group called a ballast group into the molecule or by bonding them to polymers.

The coupler may be either 4-component or 2-common to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

The compound according to the present invention is suitably used in an amount of 0.5 to 300% by weight, preferably 2 to 200% by weight based on the coupler, although it varies depending on the type of coupler used in combination. If the amount is less than this range, the effect of preventing discoloration and fading and preventing the occurrence of Y-stain is extremely small and is not suitable for practical use. However, when the compound according to the present invention is used as an antifoggant, it is used within the range of 0.5 to 2% by weight. Even if it is used, the anti-fogging effect can be expected.

On the other hand, if the amount is too large, the progress of development may be inhibited, leading to a decrease in color density.

The compound of general formula [I] used in the present invention is particularly effective in preventing discoloration and fading of magenta dye images and in preventing the occurrence of Y-stain.

As magenta couplers, 5-pyrazolone compounds are mainly used, but imidazolone compounds, cyanoacetyl compounds, and pyrazolotriazole compounds are also used. Examples are U.S. Pat. No. 2,439,098, 2,6
No. 00,788, No. 3,062,653, No. 3,
558.319, British Patent No. 956261, U.S. Patent No. 3,582,322, U.S. Patent No. 3,615,506, U.S. Patent No. 3,519,429, U.S. Patent No. 3,311, 476, U.S. Patent No. 3,419,391 , No. 3,725,067,
3.935,015, British Patent No. 1,252,418
No. 1,334.515, West German patent application (OL S
) No. 2,424,467, German Patent No. 1,810
, No. 464, Special Publication No. 44-2018, West German patent application (
01S) 2,418,959, U.S. Patent No. 2.9
83,608, German Pat. ing.

Among the magenta couplers used in the present invention, magenta couplers that give excellent results have the following general formulas [■], [
■], [IX] and [X].

General formula [■] X.

In the general formula [■], Rlo represents an anilino group, an acylamino group, or a ureido group, and x1, ■ group, sulfamoyl group, sulfonyl group, or cyano group, x4, x2, and x3 may be the same or different groups, and R11 is a hydrogen atom or an oxidized aromatic primary Represents a group that can be released by coupling reaction with an amino color developer.

General formula [■] In the general formula [■], R12 and R13 are each a hydrogen atom, an alkyl group, an alkylthio group, an aryl group, 5-
Heterocyclic group composed of 6 atoms, amino group, acyl group,
It represents an acylamino group, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, or a sulfonamide group, and R11 is as defined in the general formula [■].

General formula [rX] In general formula [IX], R, R15, and R+s are each a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
Cyano group, alkoxy group, aryloxy group, acylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
It represents a sulfamoyl group, a sulfonyl group, or an alkoxycarbonyl group, and R11 is as defined in the general formula [■]. Furthermore, R+5 and R16 may be linked to each other to form a 5-, 6-, or 7-membered ring other than an aromatic ring, and R+
s and R+s may each be a halogen atom.

The following is a blank general formula [X] In the general formula [X], R+o and Rlt are as defined in the general formula [■], and R17 is a hydrogen atom or a straight chain having 1 to 35 carbon atoms, preferably 1 to 22 carbon atoms. represents a branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, cyclic alkenyl group, aryl group, and heterocyclic group.

Next, specific examples of magenta couplers useful in the present invention will be shown, but the present invention is not limited thereto.

The following margins are: 9 -1O M-13 M-17 The amount of these magenta couplers added is 1 per mole of silver.
．． Preferably, the range is from 5X 10" moles to 2 moles, more preferably from 1 X 10" moles to 5X10" moles.

Specific examples of yellow coloring couplers are given in U.S. Patent No. 2.875.
No. 057, No. 3,285,506, No. 3,408
, No. 194, No. 3,551,155, No. 3,582
, No. 322, No. 3,725,072, No. 3,891
, 445, West German Patent No. 1,547,868, West German Application Publication No. 2,219,917, West German Patent Application No. 2,261,361,
2,414.006, British Patent No. 1,425,02
No. 0, Special Publication No. 1978-10783, Japanese Patent Publication No. 47-261
33@, No. 48-73147, No. 51-102636
No. 5G-6341, No. 50-123342, No. 5G-130442, No. 51-21827, No. 50
-87650, 52-82424, 52-11
It is described in No. 5219, etc.

A specific example of a cyan coupler is U.S. Pat. No. 2,369,92.
No. 9, No. 2,434,272, No. 2,474,2
No. 93, No. 2,521.908, No. 2,895,
No. 826, No. 3,034,892, No. 3.311,
No. 476, No. 3,458,315, No. 3,476
．． No. 563, No. 3,583,971, No. 3,591,
No. 383, No. 3,767.411, No. 4,004.9
No. 29, West German Patent Application (OLS) No. 2.414,830, OLS No. 2,454,329, JP-A-48-5H38,
No. 51-26034, No. 48-5055@, No. 51-
No. 146828, No. 52-69824, No. 52-90
No. 932, etc.

As a colored coupler, for example, U.S. Patent No. 3.476
．． No. 560, No. 2,521,908, No. 3,03
No. 4,892, Special Publication No. 44-2016, No. 38-22
No. 335, No. 42-11304, No. 44-32461
No., JP-A-51-26034, JP-A No. 52-42121, West German Patent Application (OLS) 2,418,959
You can use those listed in the No.

As a DIR coupler, for example, U.S. Pat.
, No. 554, No. 3,617,291, No. 3,70
No. 1,783, No. 3,790,384, No. 3,832
, No. 345, West German Patent Application (OLS) 2,41
No. 4,006, No. 2,454,301, No. 2.454
, No. 329, British Patent No. 953,454, Japanese Unexamined Patent Publication No. 1983
No. -69624, No. 49-122335, Special Publication No. 1977
-16141 etc. can be used.

The compound according to the present invention may be added together with a coupler to a photosensitive layer such as a silver halide emulsion layer, or may be added to a non-photosensitive layer such as an intermediate layer or a protective layer. The method of introducing the compound according to the invention into a light-sensitive layer such as a silver halide emulsion layer or a non-light-sensitive layer is similar to the method for introducing a coupler (similar method, for example, as described in U.S. Pat. No. 2,322,027). The methods described are used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.)
, phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate,
Dioctylbutyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate), esters), trimesic acid esters, etc., or organic solvents with a boiling point of 30 to 150°C,
For example, it is dissolved in a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a rough water colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

In carrying out the present invention, the following known antifading agents may be used in combination, and the dye image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

A specific example of a hydroquinone derivative is U.S. Patent No. 2.360.
．． 290@, No. 2,418,613, No. 2,67
No. 5,314, No. 2,701,197, No. 2,704
, No. 713, No. 2,728,659, No. 2,732,
No. 300, No. 2.735.765, No. 2,710.8
No. 01, No. 2,816,028, British Patent No. 1,36
No. 3,921, etc., and specific examples of gallic acid derivatives are described in US Pat.
Specific examples of p-alkoxyphenols are described in U.S. Pat. Specific examples of p-oxyphenol derivatives are described in U.S. Pat. No. 3,432,30.
No. 0, No. 3,573,050, No. 3,574.627
No. 3,764,337, JP-A-52-35633
No. 52-147434 and No. 52-152225, and specific examples of bisphenols are described in U.S. Pat. No. 3,700,455 and the like.

The following margin is the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the silver halide emulsion of the present invention).
Any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, can be used as the silver halide.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
Growth may be performed by controlling H and DAg and adding them sequentially or simultaneously. Conversion methods may be used to change the silver halide composition of the grains after growth.

When producing the silver halide emulsion used in the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. , iron salts or complex salts,
Metal ions can be added to the inside of the particles and/or on the surface of the particles, and by placing them in an appropriate reducing atmosphere, one nucleus of a reduced layer can be added to the inside of the particles and/or on the surface of the particles. .

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of the halide trowels, or they may be left in the emulsion. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may consist of different layers.

The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention can be prepared chemically by conventional methods.
1 sensitized. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods and the like can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide is used during and/or at the end of chemical ripening and/or after the end of chemical ripening. Compounds known in the photographic industry as antifoggants or stabilizers can be added before coating the emulsion.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic co-hydrophilic polymers such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers may also be used. can.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Ru. It is desirable to add a hardening agent in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution, but it is also possible to add a hardening agent to the processing solution. .

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic material of the present invention.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic material of the present invention may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, a D-phenylenediamine derivative or an aminophenol derivative) in the color development process. A dye-forming coupler is used that forms a dye. The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler in the blue light-sensitive emulsion layer. , a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler r is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides); examples of magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-virazolone couplers, pyrazolobenzimidazole couplers, and pyrazone. Examples include triazole, open-chain acylacetonitrile couplers, and cyan dye-forming couplers include naphthol couplers and phenol couplers.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Also, these dye-forming couplers only require reduction of two silver ions, even if they are 4-equivalent, meaning that four silver ions need to be reduced to form one molecule of dye. Either 2-equivalence may be used.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. It can be appropriately selected depending on the chemical structure of the hydrophobic compound. The oil-in-water emulsion dispersion method can be applied to conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a high boiling point organic solvent having a boiling point of about 150°C or higher, and if necessary, a low boiling point and/or Dissolve using a water-soluble organic solvent, emulsify and disperse using a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After that, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling organic solvents include phenol derivatives, phthalate esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, etc. that do not react with the oxidized form of the developing agent. Organic solvents are used.

Anionic surfactants, nonionic surfactants, cations are used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water using a machine or ultrasound. A surfactant can be used.

Between the emulsion layers of the silver halide photographic light-sensitive material of the present invention (same as -
(between color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity,
Color antifogging agents are used to prevent deterioration of sharpness and noticeable graininess.

The antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

To prevent the hydrophilic colloid layers such as the protective layer and middle @ layer of the silver halide photographic light-sensitive material of the present invention from fogging due to discharge caused by charging of the light-sensitive material due to friction, etc., and to prevent image deterioration due to UV light. may contain an ultraviolet absorber.

The silver halide photographic material of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is matted with the aim of reducing the gloss of the light-sensitive material, increasing the ease of writing, and preventing mutual sticking of the light-sensitive materials. agent can be added.

A lubricant can be added to reduce the sliding friction of the silver halide photographic material of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to the silver halide photographic material of the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Other hydrophilic colloid layers may contain various additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitizing). Surfactants are used.

The photographic emulsion layer and other layers of the silver halide photographic light-sensitive material of the present invention are a baryta layer or an α-olefin polymer, a flexible reflective support such as paper laminated with a synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, etc. It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide photographic material of the present invention can be improved in adhesion, antistatic properties, and dimensional stability directly or on the surface of the support after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. , may be coated via one or more subbing layers to improve abrasion resistance, hardness, antihalation properties, frictional properties, and/or other properties.

When coating the silver halide photographic material of the present invention, a binder may be used to improve coating properties. Particularly useful coating methods are exterior coating and curtain coating, which allow two or more layers to be applied simultaneously.

The silver halide photographic material of the present invention can be exposed to electromagnetic waves in a spectral region to which the emulsion layer constituting the silver halide photographic material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps,
Light emitted from phosphors excited by mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, X-rays, gamma rays, alpha rays, etc. , any known light source can be used.

Exposure times include not only exposure times of 1 millisecond to 1 second, which are normally used in cameras, but also exposure times shorter than 1 microsecond, such as 100 microseconds to 100 microseconds using a cathode ray tube or xenon flash lamp.
Exposures of 1 microsecond can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The silver halide photographic material of the present invention can be used to form an image by color development as known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include amine phenol and p-phenylene diamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally present in a concentration of about 0.1 g to about 30Q for color developer 11, preferably about 1 g to about 15Q for color developer 1j7.
Use at a concentration of g.

Examples of aminophenol-based developers include 〇-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful aromatic primary amine color developers are N, N'
-Dialkyl-p-phenyline diamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-p-phenylenediamine hydrochloride, 2
-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-hydroxyethylaminoaniline, 4
-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-o-
Examples include toluene sulfonate.

In addition to the 51st-class aromatic amine color developer, the color developer used in the process of the present invention contains various components that are normally added to color developers, such as sodium hydroxide, sodium carbonate, Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickening agents, and the like may optionally be included. The EIH value of this color developer is usually 7 or more, most commonly about 10.
〜about 13.

In the present invention, processing is carried out using a processing solution that has been subjected to color development processing and has a fixing ability, but if the processing solution that has the fixing ability is a fixing solution, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [ 7] Nitrilotriacetic acid sodium salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also, borate, salt II salt, acetate, carbonate, phosphate, etc.
Those known to be added to ordinary bleaching solutions, such as HIII agents, alkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid pHI consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide! A single type of buffering agent or two or more types of buffering agents may be included.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the storage tank for the bleach-fix replenisher, if desired, or an appropriate oxidizing agent may be added. For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

In the following margin [Examples] The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Gelatin (15,0 Peng 1; J/10100c), exemplary magenta coupler M-2 (6,01 (1/100)
0T11') to dibutyl phthalate (4,5111Q
/ 100 (ji') and emulsified and dispersed an excellent green-sensitive silver chlorobromide emulsion (silver bromide 80 mol%, coated silver 13.8B
/ 100c7. , *), coated, and dried to obtain Sample 1.

Sample 1 was applied in the same manner as Sample 1 except that when the above emulsified dispersion was prepared in the same manner, the compound of the present invention and the comparative compound were each added in an amount of 50 mol% of the coupler as shown in Table 1. ~10 were created.

Pass the sample obtained above through an optical book using the usual method.
``After exposure, the following process was performed.

[Processing process] Processing temperature Processing time Color development
Bleach and fix at 33°C for 3 minutes and 30 seconds 33
℃ Wash with water for 1 minute 30 seconds 33℃
Dry for 3 minutes 50-80℃
The components of each 2-minute treatment solution are as follows.

[Color developer] Benzyl alcohol 12-diethylene glycol 10-potassium carbonate
25a Sodium bromide
0.6g anhydrous sodium sulfite
2.0g hydroxylamine sulfate
2.5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g water was added to make 1J2, and the pH was adjusted to 10.2 with NaOH.

[Bleach-fix solution] Ammonium thiosulfate 120g Sodium metabisulfite 15 Q Anhydrous sodium sulfite 3t JEDTA ferric ammonium salt 65 Q Water was added to bring the solution to 11, and the pH was adjusted to 6.1 to 6.8.

The concentrations of Samples 1 to 10 treated above were measured using a densitometer (model KD-7R manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions.

Each of the above-mentioned treated samples was irradiated with a xenon fade meter for 5 days, and the light fastness of the dye image and the Y-stain of the uncolored area were examined, and the obtained results are shown in Table 1. However, the evaluation of each item of light resistance of the dye image is as follows.

[Residual rate] Percentage of dye remaining after side light test at initial density 1.0.

[Y-stin] From the concentration of Y-stin after the secondary light test, the Y-stin before the incident light test
- minus the concentration of Stain.

[Degree of discoloration] (yellow density) after side light test at initial density 1.0/
(magenta density) to (ye 0-density) / before the light emission test
(magenta density), and the larger this value is, the easier it is to change the color tone from magenta to yellowish. (The dye image formed from the magenta coupler used in this example tends to change to a yellowish tone due to light.) Below is a margin comparison compound (a) (a compound described in JP-A-59-180557). ) As is clear from Table 1 below, it can be seen that the compounds of the present invention are more effective than the comparative compounds in preventing discoloration and fading of magenta dye images and preventing the occurrence of Y-stain.

Example 2 In Example-1, the compound of the present invention and the comparative compound were each added in a reduced amount of 5 mol% of the coupler, and other than that, samples 11 to 2 were coated in exactly the same manner as in Example-1.
0 was created.

The sample obtained above was treated in the same manner as in Example-1.

However, the treatment temperature was 38°C.

Table 2 shows the capri, sensitivity and maximum reflection density of the samples obtained above.

As is clear from Table 2 below, when added in small amounts to the coupler, the compounds of the present invention are superior to the comparative compounds in their ability to lower capri.

Example 3 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic light-sensitive material, and sample 21 was obtained.

1st layer: Blue-sensitive silver halide emulsion layer α-pivaloyl-α-(2,4
-dioxo-1-benzylimidazolidin-3-yl)
-2-chloro-5-[γ-(2゜4-di-t-amylphenoxy)butyramide]acetanilide at 6.81
(1/100(iTll'), blue-sensitive silver chlorobromide emulsion (
silver bromide (containing 85 mol%) is converted to silver and is 3.21 (1/
1000 m”, 3.5 mo/dibutyl phthalate
100c, Hm and gelatin 13.5mg/100
The coating was applied so that the coating thickness was 0 m'.

2nd layer: middle layer 0.5 mg of 2.5-di-t-octylhydroquinone
/ 100alt, dibutyl phthalate 0.5-1
1j/1000m' and gelatin 9.01111/
It was coated to give 100CTI+'.

3rd M=green-sensitive silver halide emulsion layer 3.5 mo/100 exemplified magenta coupler M-11
Q vl, green sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver is 2.5mg/100c11t, dibutyl phthalate is 3.0mM 100c, and gelatin is 12.0sg/100CTllf. It was painted like this.

4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-sea-butyl-5-t-butylphenyl)benzotriazole 7.0 μM 1000ml, di-butyl phthalate 8,
01 (1/1000 m'), 2,5-G[-octylhydroquinone was coated at 0.510/100 c1., and gelatin was coated at 12.011 J/100 c11 t.

5th layer: Red-sensitive silver halide emulsion layer 2-[α-(2,4-di-1-pentylphenoxy)butaneamitoco-4゜6-dichloro-5-ethylphenol as cyan coupler, 4.2H/100cBt, red Sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) was converted into silver at 3.0 mg/100 cm, tricresyl phosphate at 3.511 J/100 (jll'' and gelatin at 11,511 J/1000 m') It was painted so that

6th layer: Protective layer Gelatin was coated to a thickness of 8,010/1000 m'.

In the above sample 21, the compound of the present invention, which is a dye image stabilizer, was added to the third layer in the proportions shown in Table 3,
Multilayer samples 22 to 30 were prepared, exposed and processed in the same manner as in Example 1, and then exposed to light using a xenon fade meter.
irradiated for 0 days). The results are also shown in Table 3.

From these results, it can be seen that the color fading prevention effect of the dye image stabilizer of the present invention increases as the amount added increases. In addition, compared to sample 21, samples 22 to 30 showed extremely small discoloration in the light test, and even after the light test, the color balance for yellow and cyan images was good, making them color photographic materials with excellent color reproducibility. This was recognized.

Procedural amendment (voluntary) September 13, 1985 Patent application No. 129567 2, Title of invention Silver halide color photographic light-sensitive material 3, Relationship with the person making the amendment Patent applicant address Shinjuku, Tokyo Ward Nishi-Shinjuku 1-26-2 Name (1
27) Roku Konishi Photo Industry Co., Ltd. Representative Director Keio Benko 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 [3, Details of the invention] [Explanation] Column 6, Contents of amendment (1) rR,, Rz, Rco, page 18, line 1 of the specification,
R' and X are "fR, R,, R2, Ryu, R'
, X and l are corrected as ].

(2) In the 5th line from the bottom of No. 25 of the specification, 1-dissolved in a methanol solution is corrected to ``dissolved in a methanol solution.''

On the page

Claims (1)

[Scope of Claims] A hydroquinone compound having a group represented by the following general formula [I] and/or a hydroquinone compound having a group represented by the following general formula [I] and at least one of the hydroxyl groups of the hydroquinone compound having a group represented by the following general formula [I] A silver halide color photographic light-sensitive material, characterized in that it contains a compound. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X is a halogen atom, an alkyl group, an aryl group,
Heterocyclic group, hydroxy group, alkoxy group, aryloxy group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonyl group, alkoxycarbonylamino group, sulfonyl group, alkylthio group, cyano group, nitro group or represents a carboxyl group, l represents an integer of 0 to 4, m is 1
Represents an integer between ~2. ]