JPH0612421B2 - Silver halide photographic light-sensitive material - Google Patents

Description

The present invention relates to a photographic light-sensitive material, and in particular, a silver halide color photograph in which fading due to light and discoloration due to light in a dye image obtained by developing after exposure are prevented. It relates to a photosensitive material.

The first aromatic compound in the silver halide color photographic light-sensitive material
It is known to develop exposed silver halide grains with a primary amine compound and to form a dye image by reacting the resulting oxidation product of an aromatic primary amine compound with a coupler to obtain a color image. ing.

In this method, a compound having an open-chain active methylene group is generally used as a yellow coupler for forming a yellow dye, and a pyrazolone nucleus or a pyrazone nucleus having a closed active methylene group is generally used as a magenta coupler for forming a magenta dye. A compound having a zolinobenzimidazole nucleus or an indazolone nucleus is used, and each of these forms an azomethine dye by a reaction with an oxidation product of an aromatic primary amine compound. On the other hand, as a cyan coupler for forming a cyan dye, a phenol-based compound or an α-naphthol-based compound having a phenolic hydroxyl group is generally used, and these are reacted with an oxidation product of an aromatic primary amine compound to form indoaniline. Form a dye.

It is desired that the dye image obtained from such a coupler does not fade even when exposed to light for a long time or stored under high temperature and high humidity.

However, the fastness of these dye images mainly to ultraviolet rays or visible rays is not yet satisfactory, and it is well known that they are easily discolored when exposed to these active rays. In order to remove such defects, various couplers with less fading than before are selected and used, or a method of using an ultraviolet absorber to protect the dye image from ultraviolet rays, an anti-fading agent that prevents fading due to light are used. A method of using or a method of introducing a group imparting light resistance into a coupler has been proposed.

However, for example, in order to impart satisfactory light resistance to a dye image by using an ultraviolet absorber, a relatively large amount of the ultraviolet absorber is required, in which case the dye image is significantly contaminated due to the coloring of the ultraviolet absorber itself. There were many times when it was done. Further, even if an ultraviolet absorber is used, it has no effect in preventing the fading of a dye image due to visible light, and there is a limit to the improvement of light resistance by the ultraviolet absorber. Further known is a method of using a dye image anti-fading agent having a phenolic hydroxyl group or a group which is hydrolyzed to form a phenolic hydroxyl group, and Japanese Patent Publication Nos. 48-31256 and 48-31625,
51-30462, JP-A-49-134326 and JP-A-49-134327 disclose phenols and bisphenols, U.S. Pat.
3,069,262 describes pyrogallol, garlic acid and its esters, U.S. Pat.Nos. 2,360,290 and 4,015,990 describe α-tocopherols and acyl derivatives thereof, JP-B-52-27534, JP-A-52- 14751
No. 3,735,765 and Japanese Patent No. 2,735,765, a high-doquinone derivative, U.S. Patent Nos. 3,432,300 and 3,574,6.
No. 27 describes 6-hydroxychromans, US Pat.
It is proposed to use 5-hydroxycoumarin derivatives in the specification of 3,573,050 and 6,6′-dihydroxy-2,2′-bisspirochromans in Japanese Patent Publication No. 49-20977. These compounds certainly have an effect as an agent for preventing discoloration or discoloration of the dye, but the effect is small, or even if they have an effect of preventing discoloration, the hue becomes long-wave, and Y-
It has drawbacks such as generation of stains and the presence of these compounds lowers the color developability of the coupler.

An object of the present invention is to provide a silver halide photographic light-sensitive material containing an anti-fading agent that has an excellent anti-fading effect and does not cause a change in hue, Y-stain, or decrease the color developability of the coupler. To provide.

As a result of various studies, the present inventor has achieved the above object by using a silver halide photographic light-sensitive material characterized in that at least one layer on a support contains at least one compound represented by the following general formula [I]. Found to get.

General formula [I] (In the formula, R ₁ represents an alkyl group, R ₂ represents an alkyl group, an alkenyl group, a cycloalkyl group,
It represents an aryl group or a heterocyclic group, R ₃ represents a halogen atom, an alkyl group, an alkylthio group or a cyano group, and m represents an integer of 0 to 4. More specifically, R ₁ of the general formula [I] is a linear or branched alkyl group having 1 to 24 carbon atoms (eg, methyl group, ethyl group, isopropyl group, t-butyl group, 2-ethylhexyl group). Group, dodecyl group, t-octyl group, benzyl group, phenylethyl group, etc.). These groups may further have a substituent, and examples of the substituent include an alkyl group, an aryl group, a hydroxy group, an alkoxy group, an amino group, an alkylamino group, an acylamino group, a sulfonamide group, an aryloxy group and an alkylthio group. Group, aryltyl group, carbamoyl group, sulfamoyl group, sulfonyl group, nitro group, cyano group, halogen atom, carboxyl group, arylamino group, alkoxycarbonyl group, acyl group or acyloxy group.

More specifically, R ₂ of the general formula [I] is a linear or branched alkyl group having 1 to 24 carbon atoms (eg, methyl group, ethyl group, isopropyl group, t-butyl group, 2-ethylhexyl group). , Dodecyl group, t-octyl group, benzyl group, phenylethyl group, etc.), C3-24
Alkenyl group (eg, allyl group, 2,4-pentedienyl group, etc.), cycloalkyl group having 5 to 24 carbon atoms (eg, cyclopentyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heterocycle Group (for example, pyridyl group, imidazolyl group, tetrazolyl group, oxazolyl group, thiazolyl group, benzimidazolyl group,
A benzthiazolyl group, a benzoxazolyl group, a pyrimidinyl group, an indolyl group, a pyrrololyl group, a pyrazolyl group,
Purinyl group, quinolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, furyl group, succinimidoyl group and the like). These groups may further have a substituent, and examples of the substituent include an alkyl group, a hydroxy group, an alkoxy group,
Aryl group, acylamino group, sulfonamide group, aryloxy group, alkylthio group, carbamoyl group, sulfamoyl group, sulfonyl group, nitro group, cyano group, halogen atom, carboxyl group, amino group, arylamino group, alkylamino group, alkoxy A carbonyl group, an acyl group, an acyloxy group and the like.

Of these, preferred as R ₂ is an alkyl group.

R ₃ of the general formula [I] will be described in more detail. It is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), a linear or branched alkyl group having 1 to 24 carbon atoms (eg, methyl group, Ethyl group, isopropyl group, t-butyl group, 2-ethylhexyl group, dodecyl group, t-octyl group, benzyl group, phenylethyl group, etc., alkylthio group (for example, methylthio group, octylthio group, t-dodecylthio group, cyclohexylthio group) Group, benzylthio group, etc.) and cyano group.

These groups may further have a substituent,
As the substituent, for example, an alkyl group, a hydroxy group, an alkoxy group, an aryl group, an acylamino group, a sulfonamide group, an aryloxy group, an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a nitro group, a cyano group, It is a halogen atom, a carboxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxycarbabonyl group, an acyl group, an acyloxy group or the like.

Of these, preferred as R ₃ is a halogen atom,
An alkyl group, an alkylthio group, an acylamino group, and a sulfonamide group.

When m is 2 or more, R ₃ may be the same or different. m is preferably 0 to 2.

—OR ₂ can be at any position with respect to —SR ₁ , but is preferably ortho or para.

Typical examples of the compound represented by the general formula [I] (hereinafter referred to as “specific compound”) are shown below, but the invention is not limited thereto.

[Exemplified compound]

(1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38) (39) (40) (41) (42) (43) (44) (45) (46) (47) Representative synthetic examples of the exemplified compounds are shown below, but other compounds can be easily synthesized by reaction in the same manner.

Synthesis Example 1 [Synthesis of Exemplified Compound (6)] (A) Synthesis of p-octyloxy-t-octylbenzene 103.2 g of p-octyloctylphenol and 96.6 g of octylbromide were mixed with 400 ml of dimethylformamide, and sodium hydroxide was added. Add a solution of 22.1 g dissolved in 50 ml of water,
It was heated to 100 ° C. and stirred for 1 hour. The upper layer of the reaction solution separated into two layers was taken out, and p-octyloxy-
145.6 g of t-octylbenzene was obtained (91% yield).

(B) Synthesis of 2-octyloxy-5-t-octylphenylmercaptan 143.3 g of p-octyloxy-t-octylbenzene was dissolved in 450 ml of chloroform and cooled to 0 ° C in an ice bath.
To this, 29.9 ml of chlorosulfonic acid was added dropwise over 1 hour. After the dropping, the ice bath was removed and the mixture was stirred for 1 hour, 42 ml of phosphorus oxychloride and 45 ml of dimethylformamide were added, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, the mixture was poured into 500 ml of ice water, 500 ml of ethyl acetate was added, and the ethyl acetate layer was separated. The ethyl acetate layer was washed with water, dried and concentrated to give 188 g of 2-octyloxy-5-t-octylbenzenesulfonyl chloride as a yellow viscous liquid. Ice on this 8
40 g and then 173 ml of concentrated sulfuric acid were added, the mixture was heated to 80 ° C., and 130 g of zinc was added little by little with stirring. After that, the mixture was stirred at 80 ° C. for 1 hour, zinc was removed, and the mixture was put into 500 ml of ice water.
300 ml of ethyl acetate was added, the ethyl acetate layer was extracted, dried and concentrated to give 2-octyloxy-5- as a pale yellow liquid.
150.4 g of t-octylphenyl mercaptan was obtained (yield 50%). This product was used in the next reaction without purification.

(C) Synthesis of Exemplified Compound (6) 2-Octyloxy-5-t obtained as described above
-Octylphenyl mercaptan 7g and methanol 30ml
Then, 4 g of a 28% methanol solution of sodium methylate and 3.1 g of methyl iodide were added, and the mixture was stirred for 2 hours. The lower layer of the reaction solution separated into two layers was taken out and purified by silica gel chromatography using n-hexane as a developing solvent to obtain 3.1 g of a colorless liquid (yield 43%).

Identification of this substance by FD mass spectrum and NMR confirmed that it was the same as the exemplified compound (6).

Synthesis Example 2 [Synthesis of Exemplified Compound (7)] To 6.2 g of 2-dodecyloxy-5-methylphenylmercaptan synthesized in the same manner as in Synthesis Example 1, 30 ml of methanol and 4 g of 28% methanol solution of sodium methylate were added. Then, 3.1 g of methyl iodide was added and stirred for 2 hours, and the precipitated solid was filtered and washed with methanol to obtain 4.4 g of white crystals (yield 68%).

When this substance was identified by FD mass spectrum and NMR, it was confirmed to be the same as Exemplified compound (7).

In the present invention, the specific compound is used as at least one of layers constituting the silver halide photographic light-sensitive material, that is, a protective layer, a silver halide emulsion layer, an intermediate layer, a filter layer, an undercoat layer, an antihalation layer, and other auxiliary layers. It is contained in one layer, preferably in a silver halide emulsion layer, and most preferably in a silver halide emulsion layer containing a magenta coupler. In this case, the addition amount of the specific compound is appropriately 0.1 mol to 4 mol, preferably 0.5 mol to 3 mol, per 1 mol of the magenta coupler.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative and positive film, a color photographic paper, and the like, and is particularly excellent when a color photographic paper used for direct viewing is used. The effect is exerted effectively.

The silver halide photographic light-sensitive material of the present invention, including this color photographic paper, may be monochromatic or polychromatic. In the case of a multi-color silver halide photographic light-sensitive material, a silver halide emulsion layer and a non-light-sensitive layer usually containing magenta, yellow and cyan couplers as photographic couplers in order to perform color reduction method color reproduction. Has a structure in which it is laminated on the support in an appropriate number of layers and layer order, but the number of layers and layer order may be appropriately changed depending on the priority performance and the purpose of use.

A silver halide emulsion is used for forming the silver halide emulsion layer in the silver halide photographic light-sensitive material of the present invention.
The silver halide emulsion used here includes any silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, which are used in ordinary silver halide emulsions. Any thing can be used.

The silver halide grains used in the silver halide emulsion may be those obtained by any of the acidic method, the neutral method and the ammonia method. The particles may be grown at one time,
The seed particles may be grown and then grown. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or either one may be present and the other may be mixed. Further, while considering the critical growth rate of the silver halide crystal, halide ions and silver ions may be sequentially and simultaneously added while controlling PH and pAg in the mixing vessel to grow the crystals. After growth, the conversion method may be used to change the silver halide composition of the grains.

During the production of the silver halide, a silver halide solvent may be used, if necessary, to control the grain size, grain shape, grain size distribution and grain growth rate of the silver halide grains.

The silver halide grains used in the silver halide emulsion have a grain-forming step and / or a growing step,
Metal ions can be added using cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt, iron salt or complex salt, and can be included inside the particle and / or on the surface of the particle, Further, the reduction sensitizing nuclei can be imparted to the inside of the grain and / or the surface of the grain by placing in an appropriate reducing atmosphere.

The above-mentioned silver halide emulsion may remove unnecessary soluble salts after the growth of the silver halide grains is completed, or may be contained therein. The removal of nuclear salts can be carried out according to the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion may be composed of a layer whose inside and surface are uniform, or may be composed of different layers.

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

The silver halide grains used in the silver halide emulsion may have a regular crystal form, or may have an irregular crystal form such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions which are separately formed.

The silver halide emulsion is chemically sensitized by a conventional method.
That is, a sulfur-containing compound capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds. Sensing methods and the like can be used alone or in combination.

The silver halide emulsion can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dye may be used alone, but 2
You may use it in combination of 2 or more types. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, contains a supersensitizer that enhances the sensitizing effect of the sensitizing dye in the emulsion. Good.

The silver halide emulsion is chemically ripened for the purpose of preventing fog during the production process of the light-sensitive material, during storage, or during photographic processing, and / or for keeping photographic performance stable, and / or the end of chemical ripening. At any time and / or after the completion of chemical ripening, a compound known as an antifoggant or stabilizer in the photographic art can be added by the time the silver halide emulsion is coated.

As the binder (or protective colloid) of the silver halide emulsion, it is advantageous to use gelatin, but other than that, gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives,
A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a single or copolymer can also be used.

A photographic emulsion layer of a light-sensitive material using the silver halide emulsion,
The other hydrophilic colloid layer is hardened by crosslinking a binder (or protective colloid) molecule and using a hardening agent alone or in combination for increasing the film strength. The hardener is preferably added in an amount such that the light-sensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

A plasticizer may be added for the purpose of enhancing the flexibility of the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion may contain a dispersion (latex) of a water-insoluble or sparingly-soluble synthetic polymer for the purpose of improving dimensional stability. .

The emulsion layer of the silver halide color photographic light-sensitive material according to the present invention is subjected to a coupling reaction with an oxidant of an aromatic primary amine developer (eg, p-phenylenediamine derivative, aminophenol derivative, etc.) in color development processing. Dye-forming couplers are used that do the above to form dyes. The dye-forming couplers are usually selected so that for each emulsion layer a dye is formed which absorbs the light in the light-sensitive spectrum of the emulsion layer, and the blue-light-sensitive emulsion layer contains a yellow dye-forming coupler. However, a magenta dye-forming coupler is used in the green light-sensitive emulsion layer and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

As the yellow color-forming coupler, a known open-chain ketomethylene type coupler can be used. Among these, benzoylacetanilide compounds and bivaloylacetanilide compounds are advantageous. Specific examples of yellow color-forming couplers that can be used include U.S. Patents 2,875,057, 3,265,506 and 3,408,19.
No. 4, No. 3,551,155, No. 3,582,322, No. 3,725,072,
No. 3,891,445, West German patent 1,547,868, West German application publication 2,
219,917, 2,261,361, 2,414,006, UK patent
1,425,020, JP-B-51-10783, JP-A-47-26133,
48-73147, 51-102636, 50-6341, 50-123
342, 50-130442, 51-21827, 50-87650,
52-82424 and 52-115219.

As the cyan color coupler, a phenol compound, a naphthol compound or the like can be used. Specific examples thereof include U.S. Patents 2,369,929, 2,434,272, and 2,474,
No. 293, No. 2,521,908, No. 2,895,826, No. 3,034,892
No., No. 3,311,476, No. 3,458,315, No. 3,476,563,
3,583,971, 3,591,383, 3,767,411, 4,0
04,929, West German patent application (OLS) 2,414,830, 2,454,32
9, JP-A-48-59838, 51-26034, 48-5055,
51-146828, 52-69624 and 52-90932.

As a magenta color coupler, a pyrazolone compound,
Indazolone compounds, cyanoacetyl compounds, pyrazolinobenzimidazole compounds, etc. can be used. Specific examples thereof are U.S. Patents 2,600,788 and 2,369,489.
No., No. 2,343,703, No. 2,311,082, No. 3,152,896,
No. 3,519,429, No. 3,062,653 and No. 2,108,573.

Further, a colored coupler having a color correcting effect, and further, a development inhibitor releasing coupler (so-called DIR coupler) can be used together with the above coupler in order to improve image quality.

It is desirable that these dye-synthesizing couplers have a group having a carbon number of 8 or more, which makes a coupler called a ballast group non-diffusible in the molecule. Further, these dye-forming couplers are required to reduce 4 molecules of silver ions in order to form 1 molecule of dye, but even if they are 4 equivalents, only 2 molecules of silver ions need to be reduced. Either equivalence is acceptable.

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

As a high-boiling point oil agent, a phenol derivative that does not react with an oxidized product of a developing agent, a phthalic acid ester, a phosphoric acid ester, a citric acid ester, a benzoic acid ester, an alkylamide,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150 ℃
The above organic solvents are used.

A hydrophobic compound is dissolved in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, and as a dispersion aid when dispersed in water using a machine or ultrasonic waves, an anionic surfactant, a nonionic surfactant, a cation. A cationic surfactant can be used.

Between the emulsion layers (the same color-sensitive layers and / or different color-sensitive layers) of the color photographic light-sensitive material of the present invention, the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity or sharpness. An anti-foggant is used to prevent deterioration and conspicuous graininess.

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

In the color light-sensitive material using the silver halide emulsion layer according to the present invention, an image stabilizer for preventing deterioration of the dye image can be used together with a specific compound.

The protective layer of the light-sensitive material of the present invention, a hydrophilic colloid layer such as an intermediate layer to prevent fog due to discharge caused by charging of the light-sensitive material due to friction or the like, an ultraviolet absorber to prevent deterioration of the image by ultraviolet light. May be included.

Examples of the image stabilizer include, for example, U.S. Pat.
0, 2,418,613, 2,675,314, 2,701,197,
2,704,713, 2,728,659, 2,732,300, 2,7
35,765, 2,710,801, 2,816,028, British Patent 1,
Hydroquinone derivatives described in 363,921, gallic acid derivatives described in U.S. Pat.Nos. 3,457,079, 3,069,262, etc., U.S. Pat. P-Alkoxyphenols, US Pat. Nos. 3,432,300 and 3,573,050
No. 3,574,627, No. 3,764,337, JP-A-52-35633
Nos. 52-147434 and 52-152225, and p-oxyphenol derivatives described in U.S. Pat. No. 3,700,455.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, US Pat. No. 3,533,79).
4), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, US Pat.
705,805 and 3,707,375), butadiene compounds (for example, those described in US Pat. No. 4,045,229),
Alternatively, benzoxoxide compounds (eg US patents
Those described in No. 3,700,455) can be used. Further, those described in US Pat. No. 3,499,762 and JP-A-54-48535 can also be used.

The silver halide photographic light-sensitive material according to 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 emulsion layers may contain a dye which is bleached or bleached from the light-sensitive material during the development processing.

In the photographic light-sensitive material of the present invention, the silver halide emulsion layer using the silver halide emulsion and / or other hydrophilic colloid layer can reduce the gloss of the light-sensitive material, enhance the writing property, and prevent the light-sensitive materials from sticking to each other. A matting agent can be added for the purpose of prevention.

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

An antistatic agent for the purpose of antistatic agent can be added to the silver halide photographic light-sensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, or a protective colloid other than the emulsion layer and / or the emulsion layer on the side of the support on which the emulsion layer is laminated. You may use it for a layer.

The photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention and /
Or, for other hydrophilic colloid layers, for the purpose of improving coating properties, antistatic properties, improving slipperiness, emulsifying dispersion, preventing adhesion, and improving photographic properties (such as acceleration of development, hardening, and sensitization),
Various surfactants are used.

The photographic emulsion layer and other layers of the silver halide photographic light-sensitive material of the present invention include a baryter layer or a paper laminated with an α-olefin polymer or the like, a flexible support such as synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, poly. Vinyl chloride, polyethylene terephthalate, polycarbonate,
It can be applied and formed on a film made of a semi-synthetic or synthetic polymer such as polyamide, or a rigid body such as glass, metal or pottery.

The silver halide photographic light-sensitive material of the present invention is, if necessary, subjected to corona discharge, ultraviolet irradiation, flame treatment or the like on the surface of the support, and then directly or on the surface of the support, antistatic property, dimensional stability It may have one or more subbing layers to improve abrasion resistance, hardness, antihalation properties, friction properties, and / or other properties.

In forming the silver halide photographic light-sensitive material of the present invention,
At the time of applying the material liquid for forming each layer, a thickener may be used to improve the applicability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material has sensitivity. As the light source for exposure, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam, X-ray, Any known light source or light such as light emitted from a phosphor excited by γ-rays or α-rays can be used.

The exposure time is, of course, from 1 millisecond to 1 second which is usually used in a camera, and it is also possible to use exposure shorter than 1 microsecond, for example, 100 microsecond to 1 microsecond using a cathode ray tube or a xenon flash lamp. However, an exposure longer than 1 second is possible. The exposure may be performed continuously or intermittently.

An image can be formed by performing development or color development on the silver halide photographic light-sensitive material of the present invention by a method known in the art.

In the case of performing color development, known aromatic primary amine color developing agents used in color developing solutions are widely used in various caterographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. These compounds are generally used in the color developer 1 in an amount of about 0.1 g to about 3 g.
0 g concentration, preferably about 1 g for Color Developer 1
Used at a concentration of about 1.5 g.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol and 5-amino-2.
-Oxytoluene, 2-amino-3-oxytoluene,
2-oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful primary aromatic amino color developing agents are N, N '.
It is a -dialkyl-p-phenylenediamine compound, and the alkyl group and the phenyl group may be substituted with any substituents. 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-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N, N'-diethylaniline, 4,
-Amino-N- (2-methoxyethyl) -N-ethyl-
Examples thereof include 3-methylaniline-p-toluenesulfonate.

The color developer used in the processing of the light-sensitive material of the present invention contains various components which are usually added to the color developer in addition to the primary aromatic amine color developer, such as sodium hydroxide and carbonic acid. An alkali agent such as sodium or potassium carbonate, an alkali metal sulfite salt, an alkali metal bisulfite salt, an alkali metal thiocyanate salt, an alkali metal halide, benzyl alcohol, a water softening agent and a thickening agent can be optionally contained. . The pH value of this color developer is usually 7 or more, and most commonly about 10
~ About 13.

The photographic light-sensitive material is processed with a processing solution having a fixing ability after color development processing, and is processed with a processing solution having the fixing ability. When the processing solution having the fixing ability is a fixing solution, Before that, a bleaching process is performed. As the bleaching agent used in the bleaching step, a metal complex salt of an organic acid is used, and the metal complex salt oxidizes the metal silver produced by development to convert it to silver halide, and at the same time, acts to color the uncolored part of the color former. And has a structure in which a metal ion such as iron, cobalt, or copper is coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The following can be given as specific representative examples of these.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotritri Sodium acetate salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent and can also contain various additives. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide, a metal salt or a chelating agent. In addition, borate, oxalate, acetate, carbonate, phosphate and other pH buffers, alkylamines, polyethylene oxides and the like, which are known to be added to ordinary bleaching solutions, can be appropriately added. .

Further, the fixer and the bleach-fixer are 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 A single pH buffer or two or more pH buffers composed of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained.

When the photographic light-sensitive material is processed while the bleach-fixing solution (bath) is supplemented with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate or sulfite. The bleach-fixing replenisher may contain these salts and be replenished to the processing bath.

Further, in order to increase the activity of the bleach-fixing solution, air or oxygen may be blown in the bleach-fixing bath and the storage tank for the bleach-fixing replenisher, if desired, or an appropriate oxidizing agent such as peroxide may be used. Hydrogen, bromate, persulfate and the like may be added appropriately.

[Specific effects of the invention]

In the silver halide photographic light-sensitive material of the present invention, since it has a layer containing a specific compound, the stability of a photographic image formed is very high, and it is particularly effective in a color photographic material utilizing a magenta coupler. Especially light, heat,
It is possible to enhance the fastness of a magenta dye image, which generally has a low fastness to humidity, and specifically, it is possible to favorably prevent discoloration with respect to light, fading, Y-stain in the uncolored portion against light, heat, and humidity. There is an effect.

[Specific Examples of the Invention]

Hereinafter, the present invention will be specifically described with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 Gelatin (15.0 mg / 100 m ² ) on a paper support laminated on both sides with polyethylene, a magenta coupler shown below.
^{(1) (6.0mg / 100m 2} ) 2,5-di -tert- octylhydroquinone (0.8mg / 100m ²⁾ with dibutyl phthalate (5.0 mg /
100m ² ) and emulsified and dispersed, then silver chlorobromide emulsion (silver bromide
80 mol%, coated silver amount, 3.8 mg / 100 cm ² ) were mixed, coated and dried to obtain Sample 1.

After the application of Sample 1, the comparative compounds (a), (b), (c) and (d) which are conventionally known magenta image stabilizers.
Samples 2, 3, 4, and 5 were obtained in the same manner as in Example 1 except that an equimolar amount of magenta coupler (1) was added.

After the application of the sample 1, the exemplified compounds (3), (7), (10), (17), (28) as color image stabilizers,
Samples 6, 7, 8, 9, 10, 11 and 12 were obtained in the same manner except that (30) and (32) were added in an equimolar amount to the coupler (1).

Further, as a color image stabilizer, the exemplary compound (7) and the comparative compound (a) were added in equimolar amounts with the coupler, respectively.
Got three. Similarly, the exemplified compound (1
Sample 14 was obtained using 7) and the comparative compound (b).

Magenta Coupler (1) Comparative compound (a) Comparative compound (b) Comparative compound (c) Comparative compound (d) Each sample obtained above was exposed through an optical wedge according to a conventional method, and then processed in the next step.

The components of each treatment liquid are as follows.

[Color developer]

 Benzyl alcohol 12m Diethylene glycol 10m Potassium carbonate 25g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Hydroxylamine sulfate 2.5g N-Ethyl-N-β-methanesulfone amidoethyl-3-methyl-4-aminoaniline sulfate 4.5g Water In addition, it was set to 1 and the pH was adjusted to 10.2 with NaOH.

[Bleaching fixer]

 Ammonium thiosulfate 120 g Sodium metabisulfite 15 g Anhydrous sodium sulfite 3 g EDTA Ferric ammonium salt 65 g Water was added to adjust pH to 6.7-6.8.

The samples 1 to 13 treated as described above were measured for concentration under the following conditions using a densitometer (KD-7R type, manufactured by Konishi Rokusha Kogyo Co., Ltd.).

Each treated sample was irradiated with a xenon fade meter for 10 days, and the light resistance of the dye image and the Y-stain of the uncolored portion were examined. Specifically, the density change (M density change) when the density of the magenta dye image portion before the test was set to 1.0 and the yellow coloring density change (Y-stain) in the white background portion were examined. The results obtained are shown in Table 1.

As is clear from Table 1, Samples 6 to 14 prepared by using the specific compound showed discoloration of the dye image due to light and light as compared with the case of using the conventionally known dye image stabilizer. It is understood that the fading is small and the uncolored Y-stain is also small. It is also understood that when a specific compound and a conventionally known color image stabilizer are used in combination, the fading of the dye image is further improved.

Example 2 The following layers were sequentially coated on a paper support laminated on both sides with polyethylene to prepare a multicolor silver halide photographic light-sensitive material, and a sample 15 was obtained.

First 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 was converted to 6.8 mg / 100 cm ² , and a blue-sensitive silver bromide emulsion (containing 85 mol% of silver bromide) was converted to silver. hand
3.2 mg / 100 cm ² , dibutyl phthalate was applied at 3.5 mg / 100 cm ^2, and gelatin was applied at an application amount of 13.5 mg / 100 cm ² .

Second layer: intermediate layer 2,5-di-t-octylhydroquinone 0.5 mg / 100c
m ² , dibutyl phthalate 0.5 mg / 100 cm ² and gelatin
It was applied so that the amount would be 9.0 mg / 100 cm ² .

Third layer: green-sensitive silver halide emulsion layer The magenta coupler (1) was 3.5 mg / 100 cm ² , and the green-sensitive silver bromide emulsion (containing 80 mol% of silver bromide) was 2.5 mg / 10 in terms of silver.
0 cm ^2, were coated with a dibutyl phthalate 3.0 mg / 100 cm ² and gelatin so that 12.0 mg / 100 cm ^2.

Fourth layer: intermediate layer An ultraviolet absorber of 2- (2-hydroxy-3-sec-butyl-5-t-butylphenyl) benzotriazole was added to 0.2%.
7 mg / 100 cm ² , di-butyl phthalate 6.0 mg / 100 cm ² , 2,
5-di -t- octylhydroquinone was coated so that 0.5 mg / 100 cm ² and gelatin 12.0 mg / 100 cm ^2.

Fifth layer: red-sensitive silver halide emulsion layer 2- [α- (2,4-di-t-pentylphenoxy) butanamide] -4,6-dichloro-5 as a cyan coupler
-Ethylphenol 4.2 mg / 100 cm ² , red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver 3.0 mg / 100c
m ^2, and coated with a tricresyl phosphate and 3.5 mg / 100 cm ² and gelatin so that 11.5 mg / 100 cm ^2.

Sixth layer: Protective layer Gelatin was applied at a concentration of 8.0 mg / 100 cm ² .

In Sample 15 above, a dye image stabilizer selected from a specific compound was added to the third layer in a ratio as shown in Table 2, multilayer samples 16 to 24 were prepared, and exposed in the same manner as in Example 1, After the treatment, a light resistance test (a xenon fade meter was irradiated for 15 days) was performed. The results are also shown in Table 2.

From the above results, according to the present invention, the use of the specific compound as the image stabilizer is effective in stabilizing the dye image by the magenta coupler, and the result becomes larger as the addition amount increases. Further, in the sample of the present invention, discoloration of magenta dye,
It can be seen that the fading is small, the color balance is good with the yellow and cyan couplers as the entire color photographic material, and the color reproducibility is extremely good.

Front page continued (72) Inventor Yutaka Kaneko 1 Sakura Town, Hino City, Tokyo, Konishi Roku Photo Industry Co., Ltd. (72) Inventor Kenji Kadokura 1, Sakura Town, Hino City, Tokyo Roku Konishi Photo Industry Co., Ltd. (56 ) Reference JP-A-53-53321 (JP, A) US Pat. No. 4144071 (US, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material, characterized in that at least one layer on a support contains at least one compound represented by the following formula (I). General formula [I] (In the formula, R ₁ represents an alkyl group, R ₂ represents an alkyl group, an alkenyl group, a cycloalkyl group,
It represents an aryl group or a heterocyclic group, R ₃ represents a halogen atom, an alkyl group, an alkylthio group or a cyano group, and m represents an integer of 0 to 4. )