JPS5847702B2 - color - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photographic light-sensitive material, and more particularly to an internal color photographic light-sensitive material containing a diffusion-resistant color antifoggant and at least one antioxidant of the above compounds. It is related to.

In a color photography method in which a dye is formed by coupling an aromatic primary amine developing agent and a color coupler,
A method of adding a color coupler to an emulsion layer and a method of adding it to a developer are known.

In the former case, that is, when color-developing the internal color photographic light-sensitive material in a color developer, color fogging or staining tends to occur.

It is believed that this is because the developing agent is oxidized under the influence of oxygen in the air, and this oxidized developing agent non-selectively couples with the color coupler in areas that are not exposed to light.

In order to prevent such color fogging or staining, it has been proposed to add a diffusion-resistant hydroquinone derivative to color photographic materials.

For example, U.S. Patent No. 2,360,290 includes 2.5-
Dialkylhydroquinones are described as being effective in preventing such color fogging or staining.

In addition to the above-mentioned US Pat. No. 2,360,290, for example, US Pat. No. 2,336,327, British Patent No. 55,775
No. 0, No. 557802, French Patent No. 885982, US Patent No. 2384658, US Patent No. 2403721, US Patent No. 2418613, US Patent No. 2675314, US Patent No. 270 1197, US Patent No. 2704713, US Patent No. 27
No. 28659, No. 2732300, No. 27357
No. 65, British Patent No. 1133500, US Patent No. 2 4 1 8 6 1
．． No. 3 describes that hydroquinone derivatives are effective in preventing color fog or staining of color photographic materials.

On the other hand, for the purpose of improving the light stability of a magenta color image obtained by coupling a 5-pyrazolone type color coupler with an aromatic primary amine developing agent, hydroxychroman derivatives such as those described in U.S. Pat. No. 3,432,300, 5-hydroxycoumaran derivatives as described in US Pat. No. 3,573,050, 6-chromanol derivatives as described in US Pat. It is known to add chroman derivatives and alkoxyphenols such as those described in Japanese Patent Application No. 45-82769 to color photographic materials.

However, when color photographic materials containing these antifading agents and 5-virazolone magenta coupler are stored at room temperature after being coated, their coloring ability gradually decreases, and the coloring ability of the film gradually decreases after about 6 months. It exhibited only about half the coloring ability of the light-sensitive material that immediately followed, and improvements were desired.

Furthermore, 5-virazolone magenta coupler is generally unstable to light and heat, and 5-virazolone magenta coupler remains in the unexposed areas or highlighted areas of the light-sensitive material in the color developing machine. yellow contamination is likely to occur.

These tendencies are particularly noticeable in light-sensitive materials containing 3-anilino-5-vilazolone magenta couplers.

As described in Japanese Patent Application No. 48-47465 (see Japanese Unexamined Patent Publication No. 49-134327), the storage stability of color photographic materials containing the above-mentioned color selection inhibitor and 5-virazolone magenta coupler was improved. Furthermore, it is extremely effective to add a diffusion-resistant hydroquinone derivative to the photographic material in order to prevent color blurring or staining.

As mentioned above, adding diffusion-resistant hydroquinone derivatives to color photographic materials is effective in preventing color fogging or staining during color development of color photographic materials, and is effective as an anti-fading agent. , 5-virazolone magenta coupler and is effective in improving the storage stability and preventing staining of color photographic materials containing 5-virazolone magenta coupler.

Diffusion-resistant no-hydroquinone derivatives used for these purposes are generally high-boiling organic solvents with a boiling point of about 180° C. or higher, such as methyl phthalate, ethyl phthalate, probyl phthalate, n-butyl phthalate, di-n-butyl phthalate. , alkyl esters of phthalic acid such as n-amyl phthalate, isoamyl phthalate, and dioctyl phthalate, alkylamides such as N-N diethyl laurylamide, tri-t-octyl melitate esters, polyphenyl phos Phosphate, such as tricresyl phosphate, dioctyl butyl phosphate, cyclocitric acid ester of acetyltributyl citrate, or a low boiling organic solvent with a boiling point of about 30° C. to about 150° C., such as ethyl acetate, acetic acid. After dissolving in a lower alkyl acetate such as butyl, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in any known photographic hydrophilic colloid.

These high boiling point organic solvents and low boiling point organic solvents may be mixed and used, or the hydroquinone derivative and color coupler may be dissolved in these organic solvents and then dispersed in a photographic hydrophilic colloid. It doesn't matter.

These hydrophilic colloids include, for example, gelatin,
Albumin, collodion, gum arabic, agar, cellulose derivatives, such as alkyl esters of carboxycellulose, hydroxyethyl cellulose, synthetic resins, such as amphoteric copolymers described in US Pat. No. 2,949,422, polyvinyl alcohol, polyvinylpyrrolidone, such as US Pat. No. 3,488,708. Examples include alkyl acrylates, alkyl acetoxyalkyl acrylates, and copolymers of sulfoalkyl acrylates or acrylic acids described in .

These dispersions may be added to any of the layers of the light-sensitive material, such as a silver halide emulsion layer, an intermediate layer, a filter layer, an antihalation layer, and a protective layer.

However, the above-mentioned diffusion-resistant hydroquinone derivatives have the disadvantage that they tend to be oxidized during the process of preparing the dispersion, the coating process, or the process after the coating process, causing various problems.

Therefore, one of the objects of the present invention is to prevent the oxidation of the diffusion-resistant color fog inhibitor used in internal color photographic materials, thereby suppressing the growth of colored substances and further preventing color fog and contamination. It is to prevent the precepts.

Another object of the present invention is to prevent oxidation of diffusion-resistant hydroquinone derivatives used as color antifoggants, and to prevent deterioration of the surface quality of coated materials due to oxidation.

Another object of the present invention is to provide a diffusion-resistant hydroquinone derivative which is added for the purpose of improving the storage stability of a silver halide color photographic light-sensitive material containing a 5-pyrazolone magenta coupler and a color image fading inhibitor. By preventing the oxidation of these diffusion-resistant hydroquinone derivatives, sufficient color development is maintained, and by preventing the oxidation of these diffusion-resistant hydroquinone derivatives, the surface quality of the coated product is not deteriorated.

Furthermore, another object of the present invention is to provide an internal color photographic material according to the above object, and another object is to provide a method for producing the internal color photographic material. It is.

Other objects of the invention will become apparent from the following description of the specification.

The object of the present invention is to contain at least one type of diffusion-resistant color strength anti-blurring agent represented by the following general formula (I) and at least one antioxidant selected from 1) to (7) below. This breakthrough was achieved with internal color silver halide photographic materials.

That is, in an internal color photographic light-sensitive material containing at least one type of diffusion-resistant color antifoggant, the material contains at least one type of diffusible antioxidant for stabilizing the diffusion-resistant antifoggant. More specifically, the diffusible antioxidant can be applied to the diffusion-resistant color antifoggant simultaneously or separately in a process prior to the coating process, such as an emulsifying and dispersing process, or a process of adjusting the coating liquid. In order to achieve the object of the present invention, it is preferable to add the above-mentioned compounds.

Preferably, at least one diffusion-resistant hydroquinone derivative and at least one diffusion-resistant antioxidant are contained as a diffusion-resistant color fogging inhibitor, and more preferably diffusion-resistant hydroquinone At least one type of diffusible antioxidant is allowed to coexist in at least one of the hydrophilic colloid photographic layers containing at least one type of derivatives,
More preferably, at least one of the hydrophilic colloid photographic layers constituting the color photographic material contains at least one diffusion-resistant hydroquinone derivative and at least one diffusible antioxidant. It is to contain it as an emulsified dispersion.

There is no particular restriction on the amount of the diffusible antioxidant used in the present invention, but it is effective at about 0.0001 mol to about 1.0 mol per 1 mol of the total amount of the diffusible hydroquinone derivatives. The amount is preferably about 0.001 mol to about 0.5 mol per mol.

That is, when a diffusible antioxidant is used, it is effective even when added in a small amount, probably because it is distributed uniformly due to its diffusibility.

That is, the stabilizing effect of the diffusible antioxidant on the diffusible color antifoggant agent is, for example, ``(1) The color strength antifogging effect was enhanced.

This is thought to be because deterioration of the diffusion-resistant color antifoggant agent itself due to autooxidation is suppressed.

(11) Generation of crystalline substances due to oxidation of the diffusion-resistant color antifoggant is almost or completely eliminated.

That is, for example, diffusion-resistant hydroquinones used as color antifoggants are converted by autooxidation into quinone bodies with low solubility and easy to crystallize, and these crystal bodies deteriorate the coated surface quality of photosensitive materials.

In this case, a small amount of coexisting diffusible antioxidant appears to prevent autoxidation of the diffusible hydroquinones.

Furthermore, adding a diffusive antioxidant to the coexistence system of (m) 5-virazolone magenta coupler, a color image fading inhibitor, and a diffusion-resistant hydroquinone derivative not only has the effect of preventing color fogging, but also improves the magenta coupler. Improved color development.

” etc. R represents an alkyl group having 1 to 18 carbon atoms, and R/ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms;
8 represents an alkyl group and is bonded to the 5th or 6th position.

The diffusible antioxidants used in the present invention are as follows.

(1) Sodium bisulfite (2) Ascorbic acid compounds (1) to (7) are known from the Beilstein series, and many of these antioxidants are commercially available and well-known. ℃゛So I dare not write about the law.

Diffusion-resistant color antifoggants used in the present invention include diffusion-resistant polymers having a hydroquinone moiety as described in U.S. Pat. Nos. 2,710,801 and 2,816,028, and U.S. Pat.
No. 327, No. 2384658, No. 2403721
No. 2418613, No. 2675314, No. 2701197, No. 2704713, No. 27
No. 28659, No. 2732300, No. 27357
No. 65, No. 2418613, British Patent No. 55775
0, No. 557802, No. 1156167, French Patent No. 885982, etc.
- Aromatic dihydroxy compounds containing hydroquinone derivatives, etc. can be mentioned.

Specific compounds of the diffusion-resistant color antifogging agent of the present invention include the following, but are not limited to these compounds.

The amount of diffusion-resistant no-hydroquinone derivatives applied to each hydrophilic colloid layer is about 0.0001 to about xoP/
m” is effective, preferably about 0.001 to about 3
g/m2.

The diffusible antioxidant of the present invention can be dissolved and dispersed together with a diffusion-resistant color antifoggant, coupler, etc., but it can also be dissolved and dispersed alone.

The method of adding it to the hydrophilic colloid varies depending on the type of diffusible antioxidant used, but for example, (1) U.S. Pat.
322027, such as high-boiling water-insoluble organic solvents with a boiling point of about 180° C. or higher, such as methyl fucrate, n-butyl phthalate, di-n-butyl phthalate, isoamyl phthalate and dioctyl phthalate. Alkyl esters of phthalic acid, such as N
- Alkylamides such as N-diethyl laurylamide, phosphoric acid esters such as tricresyl phosphate, dioctyl butyl phosphate, etc., or boiling points of about 30
These high-boiling water-insoluble organic solvents are dissolved in low-boiling organic solvents at a temperature of 150°C to 150°C, such as ethyl acetate, butyl acetate, secondary butyl alcohol, methyl isobutyl ketone, etc., and then dispersed in hydrophilic colloids. A low boiling point organic solvent is used in combination as necessary to dissolve and disperse in the hydrophilic colloid.

(11) Adding a diffusible antioxidant directly to the aqueous hydrophilic colloid solution.

(;**) It is dissolved in a water-miscible organic solvent such as methanol, ethanol, acetone, dimethylformamide, pyridine, dioxane, etc., and then added to the aqueous hydrophilic colloid solution.

(IV) Dissolve in an acid or alkaline aqueous solution and then add to the hydrophilic colloid aqueous solution.

An addition method such as dissolving in a surfactant aqueous solution and adding it can be used.

Furthermore, an aqueous hydrophilic colloid solution containing such a diffusible antioxidant or an aqueous solution of the above-mentioned diffusible antioxidant may be added to the coating liquid at the stage of preparing the coating liquid.

The diffusion-resistant color antifogging agent and the diffusive antioxidant of the present invention can be used in photosensitive color photographic materials such as silver halide emulsion layers, intermediate layers, protective layers, yellow filter layers, antihalation layers, etc. It may be added to any of the hydrophilic colloid layers comprising.

In this case, it may be emulsified and dispersed together with a color coupler.

The diffusible antioxidant may be added to the same layer as the diffusion-resistant color antifoggant, or may be added to a separate layer.

The hydrophilic colloids used in the present invention include proteins such as gelatin, albumin, and casein, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, and sugar derivatives such as starch derivatives; Examples include polyvinyl alcohol, polyN vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, and derivatives thereof.

Compatible mixtures of two or more of these colloids are used if desired.

The most commonly used of these is gelatin, but some or all of the gelatin can be replaced by synthetic or polymeric substances.

That is, an amino group as a functional group contained in the molecule,
Imino groups, hydroxyl groups, and carboxyl groups may be treated with a reagent having one group capable of reacting with them, or may be replaced with a graft polymer in which molecular chains of polymeric substances are bonded.

The photosensitive silver halide emulsions of the present invention contain silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or mixtures thereof. It is suspended in a hydrophilic colloid as described above, and is prepared according to a known and commonly used method.

For example, it is also useful to use a single jet method, a double jet method, a controlled jet method, etc. according to various methods such as an ammonia method, a neutral method, an acid method, etc.

Furthermore, two or more types of silver halogenide emulsions formed separately may be mixed.

For information on how to make emulsions, see, for example, "The Theor."
y of Photographic Process
” by C. E. K. Mees, Macmi
Published by l lan, “photographicCh
em istry ” P. Grafkides
Author, published by Fountainpress, especially described.

The photosensitive silver halide emulsion of the present invention is made of activated gelatin or US Pat. No. 1,574,944, US Pat.
and No. 2410689.

The photosensitive silver halide emulsion of the present invention is disclosed in US Pat.
Sensitization may be carried out using noble metal salts such as palladium salts or gold salts as described in No. 8060, No. 2399083, and No. 2642361.

The photosensitive silver halide emulsion of the present invention is disclosed in US Pat.
No. 9001, No. 2666761, No. 273490
It may be spectrally sensitized using cyanine or merocyanine dyes such as those described in No. 0, No. 2739964, and No. 3481742.

The photosensitive silver halide emulsion of the present invention is disclosed in US Pat.
They may be reduced sensitized with reducing agents such as stannous salts as described in US Pat. No. 7,850, or polyamines as described in US Pat.

The photosensitive silver halide emulsion of the present invention may be stabilized using an antifoggant or a stabilizer.

Examples of compounds for this purpose include azaindenes, mercaptotetrazoles, salts of noble metals such as palladium and platinum, oximes, imidazolium salts, and tetrazolium salts.

These include, for example, U.S. Pat. No. 2,444,605, U.S. Pat.
No. 6897, No. 3399987, No. 259791
No. 5, No. 3566265, No. 2694716,
Same No. 2131038, Same No. 2518698, Same No. 3
No. 369904, No. 2419974, No. 2419
No. 975, British Patent No. 623,448.

Hydrophilic colloids used in the photosensitive material of the present invention include aldehyde hardeners, methylol hardeners, 4-dioxane hardeners, aziridine hardeners, inoxazole hardeners,
It may be hardened with hardeners such as carbodiimide hardeners, active halogen hardeners, and activated vinyl hardeners.

Typical examples of these hardening agents are, for example, U.S. Pat.
No. 232764, No. 3288775, No. 2732
No. 303, No. 3635718, No. 3232763
No. 2732316, No. 2586168, No. 3103437, No. 3017280, No. 2
9 8 3 6 1. No. 1, No. 2725294,
Same No. 2725295, Same No. 3100704, Same No. 3
No. 091537, No. 3321313, No. 3543
No. 292, and British Patent Nos. 974723, 1167207, and 994869.

The light-sensitive material of the present invention may contain a plasticizer such as glycerin, sabonin or U.S. Pat.
No. 413, No. 3502473, No. 3514293
No. 3506449, No. 3539352, No. 3545974, No. 3507660, No. 34
No. 42654, No. 3475174, No. 34625
No. 20, No. 3493379, No. 3516833, No. 3516835, No. 3589906, No. 3617292, No. 3617291. 9 9
No. 3,663,229, etc. may be included.

The photosensitive material of the present invention can be used as an antistatic agent, for example, in U.S. Pat. No. 3,428,456, U.S. Pat.
No. 9375, No. 3549369, No. 355115
No. 2, No. 3552972, No. 3547643,
Same No. 3564043, Same No. 3615531, Same No. 3
No. 625695, No. 3655387, No. 3653
No. 906, No. 3655386, No. 3686368
No. 3756828, No. 3754924, etc. may be included.

The photosensitive material of the present invention can be used as a filter dye or an irradiation prevention dye as disclosed in US Pat. 2 7 4
7 8 No. 2, No. 2527583, No. 2956
No. 879, No. 3177078, No. 3252921
and Japanese Patent No. 39-22069.

These dyes can be used as required in US Pat. No. 3,282,699.
It may be mordanted by the method described in No.

The photosensitive material of the present invention is disclosed in U.S. Patent No. 2 as an ultraviolet absorber.
No. 415624, No. 3052636, No. 3074
No. 971, No. 3085097, No. 3067456
No. 3215536, No. 2719086, No. 2537877, No. 2784087, No. 28
No. 82150, No. 2875053, No. 27399
No. 71, No. 3097100, No. 3060029, No. 2632701, No. 2888346, and No. 2748021.

The photosensitive material of the present invention is used as a fluorescent whitening agent in US Pat.
No. 30738, No. 361-5544,
Compounds such as those described in British Patent Nos. 3586673 and 3434837 and British Patent Nos. 1332475, 1319763 and 1333586 may also be included.

In the light-sensitive material of the present invention, all open-chain ketomethylene-based yellow dye couplers can be advantageously used.

Typical examples include penzoylacetanilide-based couplers, hivarilacetanilide-based couplers, and the like.

All magenta dye type couplers such as pyrazolone and indazolone type are also advantageously used.

Also, all cyan dye-type couplers such as phenolics and naphthols are advantageously used.

These color couplers may have a camping leaving group on the active carbon atom at the coupling position.

It is preferable that the color coupler has a ballast group in its molecule to make it non-diffusible.

The terms "coupling-off group,""ballastgroup," and "non-diffusible" are commonly used with respect to color couplers and their meanings will be readily understood by those skilled in the art.

In order to impart diffusion resistance to the coupler, a hydrophobic group having at least 8 carbon atoms, such as an alkyl group or an alkylaryl group, can be introduced into the coupler molecule by conventional methods.

Many such hydrophobic groups are known and can be used in the present invention.

The ballast group is bonded to the coupler skeleton directly or via an amino bond, ether bond, thioether bond, carboxamide bond, sulfoamide bond, urea bond, ester bond, imide bond, carbonyl bond, sulfonyl bond, etc.

Representative examples of these ballast groups are shown below.

(1) Alkyl and alkenyl groups, such as (11
) Alkoxyalkyl group, for example (*12) Alkylaryl group, for example (tV) Alkylaryloxyalkyl group, for example (V) For example, U.S. Pat. No. 3,337,344, No. 34
18129 (vt+ alkoxyaryl and aryloxyaryl groups, e.g. 910 residues containing long chain aliphatic groups such as alkyl or alkenyl groups together with carboxyl or sulfonyl groups, e.g. Q11) esters Alkyl group substituted with a group, even if! ×) An alkyl group substituted with a heterocycle or an aryl group, such as (×) an aryl group substituted with an aryloxyalkoxycarbonyl group, such as typical diffusion-resistant ones according to the present invention, are described below. .

Generally, open-chain diketomethylene compounds are widely used as yellow couplers.

Examples thereof include, for example, U.S. Pat. No. 3,341,331;
No. 2.875057, No. 3551155, German Patent Publication No. 1547868, U.S. Patent No. 32
6550.6, 3582322, 3725
072, German Patent Publication No. 2162899, German Patent Publication No. 3369895, German Patent Publication No. 3408194, German Patent Publication No. 2057941, German Patent Publication No. 2213461, German Patent Publication No. 2219917, German Patent Publication No. 2261361, German Patent Publication No. 2263875, etc. .

As magenta couplers, 5-pyrazolone compounds are mainly used, but indazolone compounds and cyanoacetyl compounds are also used.

Examples include U.S. Pat. No. 2,439,098;
No. 600788, No. 3062653, No. 3558
319, UK Patent Publication No. 956261, US Patent No. 3582322, US Patent No. 3615506, US Patent No. 3519429, US Patent No. 331
No. 1476, No. 3419391, Patent Application 1976-21
No. 454, No. 48-56050, German Patent Publication No. 1
No. 810464, Special Publication No. 442016, Special Application No. 1973-
No. 45971, US Pat. No. 2,983,608, and the like.

Phenol or naphthol derivatives are mainly used as cyan couplers.

Examples include, for example, U.S. Pat. No. 2,369,929, U.S. Pat.
No. 5826, No. 3311476, No. 345831
No. 5, No. 3560212, No. 3582322,
Same No. 3591383, Same No. 3386301, Same No. 2
No. 434272, No. 2706684, No. 3034
892, German Patent Publication No. 3583971, German Patent Publication No. 2163811, Japanese Patent Publication No. 45-28836, Japanese Patent Application No. 48-33238, etc.

In addition, a coupler that releases a development-inhibiting compound (so-called DIR coupler) or a compound that releases a development-inhibiting compound during the color-forming reaction may be added.

Examples of these are U.S. Pat.
No. 27554, No. 3253924, No. 36172
No. 91, No. 3622328, No. 3705201, British Patent Publication No. 1201110, US Patent No. 329
No. 7445, No. 3379529, No. 363941
No. 7, Patent Application No. 48-33238, No. 48-41870
It is written in the number etc.

Two or more types of the above-mentioned couplers and the like can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, and the same compound can of course be added to two or more different layers.

Couplers and the like are introduced into the hydrophilic colloid of the photographic material by known methods.

This method is described in, for example, U.S. Pat. - Alkyl esters of phthalic acid such as butyl phthalate, n-amyl phthalate, in-amyl phthalate, and dioctyl phthalate, alkyl amides such as N-N diethyl laurylamide, triterj
- trimellitate esters such as octylmeritate, phosphoric acid esters such as polyphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, citric acid esters such as acetyl tributyl citrate, or having a boiling point of about 30°C to After dissolving in a low boiling point organic solvent of 150°C, such as 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. Dispersed in optional photographic hydrophilic colloids.

These high boiling point organic solvents and low boiling point organic solvents are used in combination, if necessary.

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

These couplers generally contain 2
X10-3 mol to 5X10' mol, preferably IXIO-2 mol to 5x10-1 mol, is added.

The photographic support to which the coating material for forming the hydrophilic colloid photographic layer according to the present invention is applied may be a planar material that does not undergo significant dimensional changes during processing, such as glass, metal, etc. depending on the purpose. Examples include hard supports such as ceramics and flexible supports.

Typical flexible supports include cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene 7/I' film, and polyethylene, which are commonly used in photographic materials. Terephthalate film, polycarbonate film,
Other materials include laminates of these materials, thin glass films, and paper.

Paper coated or laminated with baryta or α-olefin polymers, especially polymers of α-olefins having 2 to 10 carbon atoms, such as polyethylene polypropylene, ethylene butene copolymers, etc., roughening the surface as shown in Japanese Patent Publication No. 4719068. Supports such as plastic films, which have improved adhesion to other polymeric substances and printability, also give good results.

These supports may be transparent or transparent depending on the purpose of the photosensitive material.
Make choices that are opaque.

In addition, in the case of transparent products, not only colorless and transparent ones, but also dyes,
It is also possible to add pigments to make it transparent.

Opaque supports include those that are inherently opaque such as paper, transparent films to which pigments such as dyes and titanium oxide are added, or plastic films that have been surface-treated by the method described in Japanese Patent Publication No. 47-19068. It also includes paper, plastic film, etc. that have been made completely light-shielding by adding carbon black dye or the like.

When the adhesive strength between the support and the photographic emulsion layer is insufficient, a layer having adhesive properties to both is provided as an undercoat layer.

Further, in order to further improve the adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

In order to obtain a dye image of the color photographic light-sensitive material of the present invention, it is necessary to carry out processing according to conventional color processing steps after exposure.

The main processing steps basically include color development; bleaching: fixing steps.

In this case, each process may be independent, or two or more of the processes may be performed in one process using processing liquids having the respective functions.

An example is a one-bath bleach-fix solution.

Further, each step can be divided into two or more times as necessary, or a combination of color development, first fixing, and bleach-fixing can be performed.

In addition to the above, the development process may include a pre-hardening bath,
Various steps such as a neutralization bath, first development (black and white development), image stabilization bath, and water washing are combined.

The processing temperature is set within a preferable range depending on the photosensitive material and processing prescription, and may be lower than 18°C, but is often higher than 18°C.

Particularly often used is a temperature range of 20°G to 60°C, and recently, a range of 30°C to 60°C.

Note that it is not necessary that the set temperature for each step in the series of treatments be the same.

The color developing solution is an alkaline aqueous solution having a pH of 8 or more, preferably 9 to 12, and containing a compound, ie, a developing agent, whose oxidized product reacts with a color forming agent called a coupler to form a color forming product.

The above-mentioned developing agent means a compound having a primary amino group on an aromatic ring and capable of developing exposed silver halide, or a precursor forming such a compound.

For example, 4-amino-N-N diethylaniline, 3-methyl-4-amino-N·N-diethylaniline, 4-amino-N-β-hydroxyethylaniline 3-methyl-4-ami/-N-ethyl-N- β-hydroxyethylaniline 4-amino-3-methyl-N-ethyl-Nβ
-methanesulfamide ethylaniline, 4-amino-N-
N-dimethylaniline, 4-amino 3-methoxy-N-
N-diethylaniline, 4-amino-3-methyl-N-ethyl-N β-methoxyethylaniline, 4-amino-
3-Methoxy=N-ethyl-N-β-methoxyethylaniline, 4-amino-3-β-methanesulfamidoethyl-N-N-diethylaniline and their salts (e.g. sulfate, hydrochloride, sulfite) , p-toluenesulfonate, etc.) are mentioned as preferred representative examples.

Others, U.S. Patent No. 219301. No. 5,
No. 2592364, Japanese Patent Application Laid-open No. 64933, or L. F. A. By Mason, Pho
tographic Processing Crem
istry. (Focal Press-Londo
n edition, published in 1966), pages 226-229.

Moreover, the above-mentioned compounds can also be used in combination with 3-virazolidones.

Various additives are added to the color developing solution as necessary.

Typical examples include alkaline agents (e.g. alkali metal and ammonium hydroxides, carbonates and phosphates), pH adjusting or buffering agents (e.g. weak acids and bases such as acetic acid and boric acid, and their salts); Development accelerators (for example, various pyridinium compounds and cationic compounds described in U.S. Pat. Nos. 2,648,604 and 3,671,247, potassium nitrate and sodium nitrate, U.S. Pat. Nos. 2,533,990, 2,577,127, and 29,509)
Polyethylene glycol condensates and derivatives thereof as described in No. 70 etc., British Patent No. 1-020
Nonionic compounds such as borithioethers as typified by the compounds described in US Patent No. 033 and US Pat. , other organic amines such as pyridine and ethanolamine, benzyl alcohol, hydrazine, etc.), antifoggants (for example, alkali bromides, alkali iodides, and nitrobenzimidazoles described in U.S. Pat. Nos. 2,496,940 and 2,656,271). First, mercaptobenzimidazole, 5-methylbensotriazole, ■
-Phenyl-5 mercaptotel lazole, US Pat. No. 3,113,864, US Pat. No. 3,342,596, US Pat. No. 329
No. 5976, No. 3615522, No. 359719
Compounds for rapid processing liquids described in No. 9 etc., British Patent No. 9
Thiosulfonyl compounds described in No. 72211, phenazine N oxides as described in Patent Publication No. 1983, and other scientific photography handbooks, Vol. 29
47), as well as U.S. Patent No. 3161513 and U.S. Patent No. 316151.
4, British Patent No. 1030442, British Patent No. 1 1. 4
4 4 8 No. 1, same No.]. 2 5 1. 5 5
the stain or sludge inhibitor described in No. 8, or the interlayer effect promoter known from U.S. Pat. No. 3,536,487, etc.;
There are preservatives (e.g. sulfites, acid sulfites, hydroxylamine hydrochloride, form sulfite, alkanolamine sulfite additives, etc.).

Any bleaching solution containing known bleaching agents such as red blood salt, dichromate, iron(m), etc. can be used.

Also, any silver oxidizing agent that can be used in bleaching solutions can be used in the bleaching bath of the present invention.

For example, water-soluble ferricyanides (sodium ferricyanide, potassium ferricyanide, ammonium ferricyanide, etc.), water-soluble quinones (quinone, chloroquinone,
methylquinone, etc.), water-soluble ferric salts (ferric chloride, ferric sulfate, ferric thiocyanide, ferric oxalate, etc.), water-soluble cupric salts (cupric chloride, ferric nitrate, etc.) Copper, etc.), water-soluble cobalt salts (cobalt chloride, cobalt ammonium nitrate, etc.) are used.

Polyvalent cations and alkali metal complex salts of water-soluble organic acids are also preferably used.

Representative examples of organic acids include malonic acid, tartaric acid, ethylmalonic acid, malic acid, fumaric acid, cylicolic acid, thioglycolic acid, ethyliminodiprobionic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, and ethylenedithioglycolic acid. Acids, dithioglycolic acid, etc. can be mentioned.

Polyvalent cations are ferric ions, ferric ions, and cupric ions.

The iron, sodium complex salt of ethylenediaminetetraacetic acid is particularly useful as a bleaching agent.

Specific examples of bleaching solutions can be found, for example, in the Journal of t
heSociety of MotionPicur
e and Television Engineers
Magazine, vol. 61, pp. 667-701 (1.95
3 years), US Patent No. 3189452, German Patent No. 86
No. 6605, No. 966410, U.S. Patent No. 358232
No. 2, and British Journal of P
Photograph magazine, volume 107, pages 122-123 and 126 (1.966).

Fixers are used to remove soluble silver salts from photographic materials.

Any fixing solution containing a compound commonly used as a solvent for silver halide can be used.

For example, aqueous thiosulfates (sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, etc.), water-soluble thiocyanides (sodium thiocyanide, potassium thiocyanide, ammonium thiocyanide, etc.), water-soluble organic diols containing oxygen or sulfur atoms, etc. agents (3-thia 1,5-pentanediol, 3,6-dithia 1,8-
Octanediol, 9-oxer 3,6,12,15-
(tetrathia-1,17-heptatecanediol, etc.), water-soluble sulfur-containing organic dibasic acids and their water-soluble salts (ethylenebisthioglycolic acid, its sodium salt, etc.), imidazolidinethione (methylimidazolidinethione, etc.), etc. are advantageously used. Used by °C.

Also, L. F. A. Author: Mason
hicProcessing Chemistry,
pp. 187-188, FocalPress (1.
966) and L-ru.

Fixing agents are also advantageously used.

The bleaching and fixing steps can be carried out in one bath if necessary.

Use a suitable combination of the above bleaching agents and fixing agents.

Specific examples of bleach-fixing baths include, for example, German Patent No. 8666.
No. 05, US Pat. No. 3,582,322, etc.

Each treatment bath is advantageously used for cyclic regeneration.

Such methods are described, for example, in the Journal of t
heSociety of Motion Pic
ture and TelevisinoEngine
ers magazine, Vol. 81, pp. 293-295 (1972).

Silver is advantageously recovered from the fixer.

For example, the method of silver recovery is as follows:
e SoCity of Motion Pictu
re and Television Engineering
rs magazine, volume 81, pages 603-608.

The color photographic material of the present invention does not generate colored substances during storage, and does not reduce the effect of preventing color fog or staining during color development.

Further, the surface quality of the coated product does not deteriorate due to the precipitation of crystals caused by the added diffusion-resistant color antifoggant, especially the diffusion-resistant hydroquinone derivative.

Below, the present invention will be explained in more detail with reference to Examples.

Example 1 A cellulose triacetate film support having an antihalation layer containing black and white carbon black on one side was provided with a subbing layer on the other side, and silver halide was coated thereon in the following order: A multilayer color photographic material was created.

1st layer Blue sensitive layer 2nd layer Intermediate layer (1) 3rd layer Red sensitive layer 4th layer Intermediate layer (2) 5th layer Green sensitive layer 6th layer Protective layer Blue sensitive layer, red sensitive layer, green sensitive layer The couplers in each layer had the following structure, and each coupler was dissolved in a mixed solvent of dibutyl phthalate and ethyl acetate, emulsified and dispersed in gelatin, and then added to each emulsion layer.

Yellow dye coupler Cyan dye coupler ★Magenta dye coupler Structure of the spectral sensitizing dye used in the red-sensitive layer and the spectral sensitizing dye used in the green-sensitive layer, and the amount added per mole of silver The story was as follows.

Spectral sensitizing dye for red sensitive layer Spectral sensitizing dye for green sensitive layer each layer of silver, coupler The amount of gelatin applied is as follows. It was a sore throat.

A coating liquid in which liquid paraffin was dispersed in an aqueous gelatin solution was applied as a sixth protective layer.

As an intermediate layer between the second layer and the fourth layer, a coating solution prepared by adding an emulsified dispersion having the following structure to an aqueous gelatin solution is applied,
Samples 1 to 7 were made.

Sample 1 is a control that does not contain these emulsified dispersions.

Emulsified dispersion composition 10% by weight gelatin aqueous solution G-n-butyl phthalate 100ml 5rIll 2,5-G-t-octylhydro quinone the below described 2 3 dihydroxynaphthalene the below described 5% totecylbenzenesulfonic acid sodium aqueous solution 5ml 2 5 hmm t octyl high Doroquinone and H, 2.3 The amount of dihydroxynaphthalene applied is ★It was as follows.

Samples 1 to 7 immediately after coating made in this way,
These samples were left at 35° C. and 70% RH for 4 weeks, and then stepwise exposure was applied through a silver wedge using tungsten light as a light source, and then the following treatment was performed.

The fog density of each sample thus obtained was measured using a Fuji self-recording densitometer, and the results are shown in Table 3.

Treatment process Temperature Time Pre-bath 27℃ 10 seconds Wash with water for 15 seconds Color development 5 minutes 20 seconds Wash with water 〃 15 seconds First fixation 〃 1 minute Wash with water for 40 seconds Bleach 3 minutes Wash with water for 1 minute Second fixation 2 minutes Wash with water for 5 minutes Stable bath 10 seconds The strength of each treatment bath is as follows.

pre-bath solution water Soda carbonate (monohydrate) Sodium sulfate (anhydrous) Add water 1. As an office worker Color developer water Sodium hexametaphosphate Anhydrous sodium sulfite 2-amino-5-diethyl a Minotoluene hydrochloride Soda carbonate (monohydrate) potassium bromide Add water to make 1.07.

800rrLl 10.1' 5001 800rrLl 2.0g 4.01 3.0g 25.01 2. Office lady? First fixer and second fixer water 600ml Sodium thiosulfate (pentahydrate) Anhydrous sodium sulfite glacial acetic acid Boric acid potash alum Add water to make 1,000 ml.

240 1 15.1' ■2.0g 6. Cl 15.1' bleaching solution water potassium bromide Potassium dichromate 800ml 20. Og 50 grams potash alum Acetic acid sorg (trihydrate salt) glacial acetic acid Add water 1. Let's be Ol.

40. Cl 3. OI? 10.0g stable bath water 800rIll Formalin (37%) Oml polyethylene glycol (molecule 40% aqueous solution of 400) 5rIll Add water to make 10 liters.

In this case, the values of R, G, and B are the fog density of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer, respectively.

The compound 2,3-dihydroxynaphthalene of the present invention is
It can be seen that samples 3, 4, 6, and 7 used in combination with 5-di-t-octylhydroquinone had a very small increase in fog after being stored at 35° C. and 70% RH for 4 weeks.

Example 2 The same emulsified dispersion as that added to intermediate layer 2 and intermediate layer 4 in Example 1 was left in a refrigerator at 5°C for 4 weeks, then melted at 40°C, left for 24 hours, and then carried out. This was mixed with a gelatin solution in the same manner as in Example 1 to obtain an intermediate layer coating solution.

This was applied in the same manner as in Example 1, and samples 1' to 7'
I made up to.

Sample 1' is a control containing no emulsified dispersion in the intermediate layer.

These samples 1' to 7' were exposed and processed in the same manner as in Example 1, and then their fog densities were measured using a Fuji self-recording densitometer, and the results are shown in Table 4. .

Comparing the values in Table 4 with the fresh values in Table 3 shows that the compound 2,3-dihydroxynaphthalene of the present invention
Sample 3' used in combination with 5-t-octylhydroquinone
, 4l, 6', and 7l show that the increase in fog is small even when refrigerated emulsified dispersions are used in the intermediate layer.

Example 3 The following experiment was conducted to examine the antioxidant effect of the compound of the present invention.

50d of 2,5-di-t-octylhydroquinone 12
The following compounds were added as antioxidants at a concentration of 0.1 mole per mole of 2,5-di-t-octylhydroquinone, and the mixture was left at 25 °C for 10 days. , from the methanol solution of 2,5-di-t-octylhydroquinone alone, precipitation of approximately 0.1' crystals of 2,5-di-t-octylquinone was observed, whereas in the solution containing these compounds. In this case, crystal precipitation did not occur at all, or even if it did occur, it was only in a small amount.

On the other hand, we also conducted the following experiment.

A 10-3M solution of 2,5-di-t-octylhydroquinone was prepared with a mixed solvent of methanol and water (volume ratio 1:1), and various antioxidants were added to the solution of the above 2,5-di-t-octylhydroquinone. Each solution containing an amount equivalent to 1/10 mol was prepared and left at 25°C for 2 weeks.

In this solvent, the hydroquine type changes its absorption to have a peak wavelength at 297rrLμ.

Therefore, the 297 mμ of the solution of the above hydroquinone type alone
29 of solutions containing antioxidants for concentration changes in
The rate of concentration change at 7 mμ was observed.

According to this method, the antioxidant compounds 2,3-dihydroxynaphthalene, ascorbic acid, hydroquinone, hydroxylamine hydrochloride, catechol, and isoamyl gallate were effective in reducing the decrease in concentration at 297 mμ.

Example 4 A silver halide multilayer color photographic light-sensitive material was prepared by coating in the following order on photographic paper whose surface was covered with polyethylene.

1st layer Blue 2nd layer Medium 3rd layer Green 4th layer Medium 5th layer Red 6th layer Sensitive interlayer (1) Sensitive interlayer (2) Sensitive layer Protective layer Coupler of the blue sensitive layer of the first layer and The couplers for the fifth red-sensitive layer were each dissolved in a mixed solvent of dibutyl phthalate and ethyl acetate, emulsified and dispersed in gelatin, and then added to each emulsion layer.

Yellow prime coupler α-hyhaloyl-α-(5,5-dimethyl-3hytantoynyl)-2-chloro5[α-(2,4-di-t-amylphenoxy)butylamide]acetanilide for blue-sensitive layer cyan dye-formed coupler 2-[α-(2,4-G-t-amyl fenoki**)
Butylamide] 4,6 dichloro-5-methylphenol The emulsified dispersion for the green-sensitive layer of the third layer is prepared by combining liquid I and ■
It was prepared by preparing a liquid and dissolving it by heating at 60°C, then mixing the liquid (1) and the liquid (2) and stirring the mixture using a homogenizer.

This emulsified dispersion was mixed with a silver chlorobromide emulsion containing 50 mol% of bromine to form a coating solution for the third layer.

The coupler in the green sensitive layer is 1-(2,6-dichloro4-methylphenyl)-3-(3-(α-2,4-sheet
rt-amylphenoxy)butylamide] penzamide-5-pyrazolone.

Anti-fading agent a 6,6'-dihydroxy-7,7'-dimethyl 4.
4,4',4'-tetramethylbis-2,2'nupirochroman b 2,2,4-trimethyl-6-hydroxy7-t-
butylchromanhydroquinone c 2,5-di-t-octylhydroquinone d 2-methyl-5-(1'-methyl-heptadecyl)-hydroquinone antioxidant e Sodium bisulfite f Hydroxylamine hydrochloride 4th layer intermediate layer ( 2) was made by adding the following set of emulsified dispersions to an aqueous gelatin solution and coating.

2-(5-tert-2-tert chloropenzotriazo-4-gyl)-4-methyl-6-butylphenol-2) Ethyl acetate 4 0.8 6 10 g 1 rIll rrLl Gelatin 10 i Sodium bisulfite 0.02 L? Sodium dodecylbenzenesulfonate 0.2 g * * The second intermediate layer (2) and the sixth protective layer are It was made by applying an aqueous gelatin solution.

The coating amounts of silver, coupler ultraviolet absorber and gelatin in each layer of the photosensitive material thus produced were as follows.

These samples were mixed with emulsified dispersions A and B of the third green-sensitive layer.
, C, D, E, F, G, H, samples 8, 9, 1
01 11, 12, 13, 14 and 15.

Immediately after coating and after being left at room temperature for three months after coating, Samples 8 to 15 were subjected to stepwise exposure through a silver wedge using tungsten as a light source, and were subjected to the following treatments.

Treatment process Temperature Time Color development 30℃ 6 minutes Stop 2 Wash with water 2 Bleach fixing 〃 2 Wash with water 2 Stable bath 〃 2 Drying The processing solution used has the following specifications.

Color developer benzyl alcohol 1 2rrLl diethylene glycol 3. 5 ml Caustic soda Sodium sulfite Potassium bromide Sodium chloride Forager Hydroxylamine sulfate Ethylenediaminetetraacetic acid disodium dihydrate 2.0 g 2.0 g 0.4 g 1.0 g 4.0 g 20 g 2. O1 4-amino-3-methyl-N ethyl-N-(β-methanesulfonamidoethyl) aniline sesquisulfate monohydrate 5.01 Add water and stop solution Sodium thiosulfate Ammonium thiosulfate (70%) Sodium acetate Potassium acetate Add brine and add 10g 3Qcc 5g 3Qcc 151 1l Bleach-fix solution E ferric sulfate 20g ethylenediaminetetraacetic acid. thorium. Dihydrate 2Na 36g Sodium carbonate monohydrate 17te 5z 70% ammonium thiosulfate aqueous solution 100ml Formic acid 5g Adjust pH to 68, add water to 1l Stabilizing solution ★ ★ Formic acid 5? Sodium citrate 5g Sodium metaphoate tetrahydrate 3g' Potash alum 15P Add water to 1L The maximum concentration of the sample thus obtained was measured using a Fuji type self-recording densitometer, and the results are shown in the table below. Indicated.

R, G, and B in the table indicate red density, green density, and blue density, respectively.

From this table, it can be seen that the light-sensitive material containing the magenta coupler and anti-fading agent in the green-sensitive layer exhibits a decrease in coloring ability when left at room temperature for three months, whereas the sample further containing a hydroquinone derivative and It can be seen that in the sample containing an antioxidant for the hydroquinone derivative, there is no decrease in coloring ability.

On the other hand, the emulsified dispersions A to H used for the green sensitive layer were stored at 5°C for 2 weeks, left in a dissolved state at 40°C for 24 hours, and passed through P paper** having pores of about 1 μm in diameter. After one pass, the following first pass residue was obtained.

From this result, emulsified dispersion A containing a diffusible antioxidant,
B, C, D, E, G and H show less residue.

(However, emulsified dispersions C and G do not contain hydroquinone derivatives.

) This is considered to be due to the oxidation of the hydroquinone derivative being suppressed by the antioxidant effect of the antioxidant on the hydroquinone derivative.

Furthermore, using the emulsified dispersion left in this dissolved state, a coating sample was prepared in exactly the same manner as shown above.
Samples using emulsified dispersions A, C, D, E, G, and H had extremely good coating surface quality, but emulsified dispersions B and F
Samples prepared using this method showed poor coating surface quality.

The internal color photosensitive material according to the present invention includes general color silver halide photosensitive materials such as color reversal film, color negative film, color positive film, color paper, etc., as well as color direct as a silver halide photosensitive material. Positive film, monochrome light-sensitive materials, color instant photographic light-sensitive materials, especially DD
For example, British Patent No. 840731, British Patent No. 1038331, using R coupler (diffusible dye-releasing coupler);
Examples include diffusion transfer type color photosensitive materials using diffusible dye-releasing couplers as described in JP-A No. 1066352 and JP-A-473480.

Claims (1)

[Scope of Claims] 1 Contains at least one diffusion-resistant color antifoggant represented by the following general formula (I) and at least one antioxidant selected from the following (1) to (7). Internal color silver halide photographic material. R represents an alkyl group having 1 to 18 carbon atoms, and R'
represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and is bonded to the 5th or 6th position. (1) Sodium bisulfite (2) Ascorbic acid