JPS6156345A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enable a development with a small amount of a replenisher by allowing to exist at least one of silver halide emulsion layers on a surface of a base material and using a quaternary onium compd. having a water resisting property at an opposite side of the emulsion layer against the base material. CONSTITUTION:The quanternary onium compd. layer having the water resisting property exists in a back layer of the silver halide photosensitive material. The water resisting property means such a propery as not to elute the compd. into a treating liquor from the material. Namely, to give the water resisting property to the compd., it makes to increase a mol. wt. of the compd. and/or to introduce a hydrophobic group to the compd., thereby reducing an affinity for the treating liquor. As to the quanternary onium compd. having the water resisting property, the quanternary ammonium compd. having the water resisting property is the most preferable. The onium compd. is prepared by polymerizing two or more of the three compds. selected from a monomer belonging to vinylpyridine and its derivative, or a basic vinyl monomer, and primary-tertiary amines and a compd. having a haloalkyl group, and then changing an amino group contd. in the obtd. copolymer or the obtd. graft polymer to the quanternary amino group.

Description

Detailed Description of the Invention (1) Background of the Invention Technical Field The present invention relates to a silver halide photographic material. More specifically, the present invention relates to a silver halide photographic material that requires only a small amount of replenishment of a processing solution in a development process using a replenishment method.

Prior Art In recent years, there has been a demand for faster and simpler processing of silver halide photographic materials.

In particular, there is a demand for a processing method that requires only a small amount of processing solution replenishment in the development process using a replenishment method.
This allows cost reduction and the like.

In order to meet the above demands, various color developer regeneration methods have been attempted in the color development process.

For example, J, Appl, Phot, Eng,...
5, 208 (1979); Monthly Lab, 15, 113
・ (1979); SMPTE, J, 88, 1
65 (1979); J, Appl, Phot,
Eng,,5.

32 (1974): SMPTE, J., 88°16
8 (1979); JP-A No. 52-143018;
No. 2-146236; No. 53-149331; No. 54
No.-9629; J.

Appl, Phot, Eng,, 5. 2 1 6
(1979) and others.

In general, when the amount of replenishment is reduced, the amount of eluate from the silver halide photographic light-sensitive material increases, resulting in a decrease in sensitivity.Therefore, attempts have been made to raise the processing temperature to prevent the decrease in sensitivity and reduce the amount of replenishment. has also been done.

For example, Hunt's Color Paper Treatment Agent CP-L
R treatment agent Hunt Co1or Pr1nt Chem
istries (Photographic Bull
etin No. 49); Proceedings of the Photographic Society of Japan A-
Examples include the method described in ``Low Replenishment of Color Paper Processing'' (1980).

The above methods have the advantage of requiring fewer liquid preparations, but the processing liquid regeneration method requires large equipment, and the method of reducing the amount of replenishment requires
There are drawbacks such as high temperature processing being required during development processing and poor stability of the processing solution, and there is still room for improvement.

II. OBJECTS OF THE INVENTION The main object of the present invention is to avoid the above-mentioned disadvantages,
The object of the present invention is to provide a silver halide photographic material that can be developed using a small amount of replenisher in a replenishment-based development process.

Such objects are achieved by the invention described below.

In other words, unreleased! No. 51 is a halogen material having at least one silver halide emulsion layer on one surface of the support, and having a water-resistant quaternary onium compound present on the surface opposite to the surface on which the silver halide emulsion layer is formed. It is a silver oxide photographic material.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The back layer of the silver halide photographic material of the present invention contains a water-resistant quaternary onium compound.

The water-resistant quaternary onium compound used in the present invention is as described below, and water resistance means the property of not substantially eluting from the sensitive material into the processing solution during development processing.

That is, in order to impart water resistance, it is sufficient to increase the molecular weight or introduce a hydrophobic group to reduce the affinity with the processing liquid.

As the water-resistant quaternary onium compound, a water-resistant quaternary ammonium compound is most preferable; 3) Copolymerizing (1) and/or (2) and (3) of the three haloalkyl group-containing compounds, or copolymerizing (1) and/or (2) into a polyolefin film. ) and (3) are graft-polymerized.

The 7-mino group of these copolymers or graft polymers is
It is a classification.

Here, the vinylpyridine monomer in (1) refers to compounds of the following formulas (I), (II) and ([[I).

(1) (II) ([) In the above formula, R represents H, CH3, C2H5 or C3H7.

In addition, the vinyl heptamer having 7 basic amide groups in (1) is a compound of the following formula (rV), in which R1 is one selected from the group consisting of H and CH3, and R2 and R3 is H1CH3, C2R5, n-C, 3R7, CH(
One selected from the group consisting of CH3)2 and n-C4Hg, which may be the same or different, and n is 1 to 10.
is an integer between .

The amines in (2) include primary amines such as aniline, methylamine, and ethylamine, dimethylamine,
Secondary amines such as diethylamine, methylethylamine, methylphenylamine, tertiary amines such as trimethylamine, triethylamine, dimethylphenylamine, ethylenediamine, phenylenediamine, N.

Polyamines such as N'-tetramethylethylenediamine can be used.

When these compounds are copolymerized, they can react with a compound having a haloalkyl group to quaternize the amide 7 group.

Examples of the compound having a haloalkyl group in (3) include methyl iodide, ethyl bromide, propyl chloride, butyl iodide, and pentyl bromide. In addition, aromatic nuclei such as benzene nucleus and naphthalene nucleus may be introduced (wherein, X represents C1, Br or engineering, and R4 and R5 represent a hydrogen atom or an alkyl group).

These compounds react with amine compounds.

Quaternization can be performed.

In addition, instead of (1), the amine 7 group contained in the quaternized Li
(1) (7) View, Pi, Ji, System%/Two! Alternatively, a vinyl heptamer having a basic amino group may be used.

Further, instead of (3), a compound having a functional group into which a haloalkyl group can be introduced and a condensable functional group may be used as (3)'.

Such a compound specifically refers to a compound that has a vinyl group and can be substituted with halogen; more specifically, a compound that has a haloalkyl group and a vinyl group;
Or it means a compound having a haloaryl group and a vinyl group. Specific examples include halomethylstyrene, haloethylstyrene, halomethylated vinylnaphthalene, halomethylated acenaphthylene; halopensylated vinyl, and the like. Industrially, halomethylstyrene is the easiest to use.

In addition to (3), a heptamer copolymerizable with a monomer having a haloalkyl group may also be used.

Specifically, such seven materials include styrene,
There are vinyl compounds such as vinylnaphthalene, vinyl chloride, acrylonitrile, and vinyl acetate, and condensation monomers such as phenol and naphthol.

Furthermore, the method for carrying out the above polymerization or copolymerization is not particularly limited, and conventional means such as radical polymerization or ion polymerization may be used. The m-combination method can be carried out in an acidic or alkaline medium together with a condensing agent such as an aldehyde.

Further, the compound having a functional group into which a haloalkyl group can be introduced may be an ion exchange membrane.

Then, a haloalkyl group can be introduced by a conventional haloalkylation method, for example, by carrying out haloalkylation using a haloalkylating ether such as chloromethyl methyl ether or other haloalkylating reagent.

In this way, each of the above components may be copolymerized, for example, graft polymerized onto a polyolefin film.

The polymerization method may be according to a known method.

In the present invention, polyolefin-based film materials include polyethylene, polypropylene, polyethylene-propylene copolymer, poly(4-methylpentene-1), polyethylene terephthalate, polytetrafluoroethylene, poly(tetrafluoroethylene-hexafluoropropylene), Poly(tetrafluoroethylene-ethylene), polyvinylidene fluoride, poly(barfluoroalkoxy-tetrafluoroethylene-ethylene), polyvinylidene fluoride, poly(perfluoroalkoxy-
These are film-like materials such as tetrafluoroethylene) and poly(trifluoromonochloroethylene). Among these 11 linear materials, low-density polyethylene film, poly(tetrafluoroethylene-hexafluoropropylene) film, and poly(tetrafluoroethylene-ethylene) film t*m have a crosslinked structure by pre-irradiation with separable N-rays. It is suitable because it forms

To give a specific example of quaternizing an amine in the present invention, a polyolefin film is impregnated with a solution containing a vinylpyridine monomer and a vinylbenzyl halide in a molar ratio of 1 to 5.

Graft copolymerization of a vinylpyridine monomer and vinylbenzyl halide onto a polyolefin film by irradiating ionizing radiation before and/or after impregnation, and graft copolymerization onto a polyolefin film. and the N atom of the pyridine ring of the vinylpyridine monomer.

A crosslink is formed within or between molecules by covalent bonding with the halomethyl group of vinylbenzyl halide, and at the same time N
The atoms are quaternized as described below to form weak salt anion exchange groups.

As another specific example of quaternizing an amine, a basic vinyl monomer and vinylbenzyl halide are mixed in a molar ratio of 1 to 1.
The basic vinyl monomer and vinyl benzyl halide are grafted onto the polyolefin film by impregnating the polyolefin film with a solution containing a ratio of 5% and irradiating ionizing radiation before and/or after impregnation. Copolymerize and graft ff1 onto polyolefin film-like material
A crosslink is formed within or between molecules by the covalent bond between the N atom of the terminal 7-mino group of the combined basic vinyl heptamer and the halomethyl group of the vinylbenzyl halide, and at the same time the N atom is It is quaternized to form a weakly basic anion exchange group.

In the above two examples, even if there is no polyolefin-based film-like material, if a combination of a nitrogen-containing compound and a halide that can be copolymerized to form a film is selected, the polyolefin-based film-like material may not be included.

Further, as the water-resistant quaternary onium compound to be contained in the back layer, an ammonium or phosphonium compound represented by the following formula (V) may be used.

This compound is described in US Pat. No. 4,070,189.

(V) In the above formula (v), A, B, Q, R6.

R7, R8 and M represent the following.

A is an addition-polymerizable heptad unit containing at least two ethylenically unsaturated groups, e.g.
Examples include divinylbenzene, allyl acrylate, allyl methacrylate, inpropylidene diphenylene diacrylate, diethylene glycol dimethacrylate-1, ethylene diacrylate, ethylidene diacrylate, and the like.

B is a copolymerizable α,β ethylenically unsaturated heptad unit! Examples include J, Nithi, Ren, propylene, isobutyne, methylpentene, methylbutene, styrene, and the like.

Q is N or P.

R8, R7 and R8 are cyclic hydrocarbon groups or alkyl groups.

M is an anion such as halide, sulfate group, acetate group, etc.

Further, X is 0.1 to 20 mol%, y is 0 to 90 mol%, and z is 10 to 99 mol%.

, i Each of the above onium compounds may be dispersed in a wood-philic polymer such as gelatin and applied as a back layer.

For dispersion, known hardening agents, surfactants, etc. (for example, vinyl sulfone hardeners, alkylbenzenes, sulfone thread-resistant surfactants, etc.) can be used for dispersion, if necessary.

In addition, various known coating methods such as dip coating, roller coating, curtain coating, extrusion coating, etc. can be used for coating.

Further, the above-mentioned material obtained by graft polymerization on, for example, an olefin film may be used as it is as a support.

The number of fleas of the quaternary onium compound present on the back side may vary depending on the amount of silver halide applied in the silver halide photographic light-sensitive material, the amount of exposure during development, the amount of developed silver, etc., but is preferably 0.0 l. -100a+eq/rn', more preferably 0,05~50meq/rn', particularly preferably 0.1~L Orrreq/rrr
” There is a problem.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention.

The average grain size of silver halide grains in a photographic emulsion (the grain size is the grain diameter for spherical or approximately spherical grains, the ridge length is the grain size for cubic grains, and expressed as an average based on the projected area) is the grain size. The size distribution may be narrow or wide.

Silver halide grains in photographic emulsions are cubic.

It may have a regular crystal shape such as an octahedron, or it may have an irregular crystal shape such as a spherical shape or a plate shape, or it may have a composite shape of these crystal shapes. It may consist of a mixture of particles of various crystalline forms.

Silver halide grains may have different phases inside and on the surface, or they may consist of a uniform phase, and the latent image may be formed mainly on the surface, or it may be such that the latent image is formed mainly inside the grain. It may be a particle.

The photographic emulsion used in the present invention is P, C1afkide
Written by CHimie et Physique Photo
ographique (published by Pau1Mante1,
(1967), G., F. Duffin, Pho.
tographic Emulsion Ghemis
try (The Focal Press, 1966), V, L, Zelikman eta1, Making and, Coating Phot
graphicEmulsion (The Fc+
Cal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen J11 may be any one-sided mixing method, simultaneous simultaneous method, or a combination thereof. .

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium j! 2 or its complex salt, rhodium salt or its complex 43!
, iron salts, iron complex salts, etc. may be present together.

For chemical sensitization, see, for example, H. Frleser, ed.
Die Grundlagender Photogr
aphiSchenProzesse mit 5
ilber-halogeniden” (Akadem
ische Verlagsgesellschaf
T, 1988) pages 675-734 can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfur salts, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts, Pt, I
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as r, Pd, etc. can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fogging during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles,
Aminotriazoles, penztriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), etc.;
Mercaptopyrimidines; mercaptotriazines, e.g. thioketo compounds such as oxadolinthion; azaindenes, e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1°3.3a
, 7) tetraazaindenes), pentaazaindenes, etc.; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. I can do it.

Gelatin is advantageously used as a binder or protective colloid for photographic emulsions, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethylcellulose, carboxymethylcellulose, etc.
Cellulose derivatives such as sulose sulfate esters, sodium alginate, sugar derivatives such as starch derivatives: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinyl A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers such as pyrazoles.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or others.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes.

It is a pigment belonging to cyanine pigments, merocyanine pigments, and complex merocyanine pigments. These pigments include
Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus. That is, pyrroline nucleus,
Oxazoline nucleus, thiazoline nucleus, virole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and aromatic in these nuclei Nuclei in which hydrocarbon rings are fused, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazoline-2,
A 5- to 6-membered heteroartic ring nucleus such as a 4-dione nucleus, a thi'azolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbic acid nucleus can be used.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are disclosed in Research Disclosure (Res.
176 volumes +
17643 (published December 1978), page 23, ■J.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, which can form a color by oxidative coupling with an aromatic primary amine developer (e.g., phenylenediamine derivative, aminophenol derivative, etc.) during color development processing. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers include acylaceI amide couplers (
Examples of the cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule.The couplers may be either 4-equivalent or 2-equivalent to silver ions.
・I.

It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called IR coupler). Couplers may be incorporated into the silver halide emulsion layer by known methods such as U.S. Pat. No. 2,322, which may include colorless DIR coupling compounds that release development inhibitors.
, No. 027 can be used. For example, phthalate alkyl esters (e.g. digtylphthalate, dioctyl phthalate), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate) , benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., or boiling point Organic solvents with a temperature of 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, propionbutyethyl, secondary butyl alcohol,
After dissolving in methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc.
Dispersed in hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.
For example, chromium salts (chromium alum, chromium acetate, etc.),
Aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2゜3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5-1 lyacryloyl-hexahydro-s-triazine, 3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochlor, mucophenoxychloric acid, etc.), etc. can be used alone or in combination. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization), etc. Various surfactants may be included for various purposes.

Various other additives may be used in the silver halide photographic emulsion of the present invention. For example, brighteners, dyes, spectral sensitizers, desensitizers, hardeners, coating aids, antistatic agents, plasticizers,
Slip agents, attifying agents, development accelerators, oils, mordants, ultraviolet absorbers, anti-fading agents, anti-fogging agents, etc.

For these additives, please refer to RESEARCH DISCLOSE.
SURE) No. 176, pages 22-31 (RD-17643
) (Dec, 1978) can be used.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film or paper, or a rigid support that is commonly used in photographic materials.

Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose vinegar sms, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various known coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. U.S. Patent 2,681゜29
No. 4, No. 2,761,791, No. 3゜526.528
The method described in this issue is an advantageous method.

The invention is also applicable to multilayer multicolor natural color photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support.

The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer 1 contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

Furthermore, various color and black and white light-sensitive materials can be mentioned as photographic light-sensitive materials using the present invention. For example, color negative film for photography (general use, movie use, etc.)
, color reversal film (for slides, movies, etc., and may or may not contain couplers), color photographic paper, color positive film (for movies, etc.), color reversal photographic paper, color using silver dye bleaching method Photosensitive materials, photosensitive materials for plate making (lithographic film, scanner film, etc.), X-ray photosensitive materials (for direct/indirect medical use, industrial use, etc.), black and white negative film for photography, black and white photographic paper, photosensitive materials for microphotography (C0M) micro-film, etc.).

For photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. Additionally, the processing temperature is usually between 18°C and 5°C.
selected between 0°C but below 18°C or 50°C
The temperature may exceed °C. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied.

The black and white developer contains known developing agents such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p-aminophenol). They can be used alone or in combination.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, for example, phenylenediamines (for example, 4-amino-1'-N-N-di-thyl-az'-
3-methyl-4-amino-N,N-diethylaniline,
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide, thylaniline, 4-amino-3-methyl-N-ethyl-N-β
-methoxyethylaniline, etc.) can be used.

In addition, L, F, A, Mason [Photographic Φ Processing Collection].

Published by Focal Press (1966), 266-229.
Page, U.S. Pat. No. 2,193,015, 2.592.3
64, JP-A No. 48-64933, etc. may be used.

The developer may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. Contains 00 and 7゛1ki6. Also, if necessary 9. Hard water number 1 agent, preservatives such as human mixylamine, organic solvents such as benzyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts, amines. Development accelerator such as 1 dye-forming power puller,
competitive couplers, fogging agents such as sodium poron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents as described in U.S. Pat. No. 4,083,723; OLS
) No. 2.622.950 may contain antioxidants and the like.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process or separately.The bleaching agent may be 1, for example iron (■).
, cobalt (I[I), chromium (Vl), m(II)
Compounds of polyvalent metals such as, peranes, quinones, nitroso compounds, etc. are used. For example, ferricyanide,
Dichromate, organic complex salts of iron (m) or cobalt (m), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diami/-2-propaturatetraacetic acid, or citric acid, tartaric acid , complex salts of organic acids such as malic acid; persulfates, permanganates:
Nitrosophenol and the like can be used. Of these, potassium ferricyanide, sodium iron(III) ethylenediaminetetraacetate, and ammonium iron(III) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron (m) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

Bleaching or bleach-fixing sources include U.S. Pat.
No. 0, No. 3,241,966, Special Publication No. 45-8506
Bleaching accelerators described in Japanese Patent Publication No. 45-8836, etc.
In addition to the thiol compound described in JP-A-53-65732, various additives can also be added.

The processing method used in the present invention includes processing steps such as color development, bleaching, and fixing as described above. After the fixing step or bleach-fixing step, processing steps such as washing with water and stabilization are generally performed; It is also possible to use a simple treatment method such as performing only a stabilization treatment step.

The rinsing water used in the rinsing step can contain known additives, if necessary.

For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, bactericides and fungicides that prevent the growth of various bacteria and drugs, hardening agents such as magnesium salts and aluminum salts, drying load, and unevenness. A surfactant or the like can be used to prevent this. Or L, E
.

West, “Water Quality Cr
1teria” Photo.

Sci, andEng,, vol, 9 No, 6
Compounds described in Pages 344-359 (1965) and the like can also be used.

Further, the washing step may be carried out using two or more tanks 1 if necessary, and the washing water may be saved by carrying out multi-stage countercurrent washing (for example, 2 to 9 stages).

As the stabilizing liquid used in the stabilizing step, a processing liquid that can stabilize a dye image is used. For example, a solution having a buffer 11B with a pH of 3 to 6, a solution containing an aldehyde (for example, formalin), etc. can be used. Optical brighteners, chelating agents, bactericidal agents, fungicides, hardeners, surfactants, and the like can be used in the stabilizing liquid as necessary.

Furthermore, the stabilization process may be carried out using two or more cypress tanks if necessary, and the stabilizing liquid can be saved by performing multi-stage countercurrent stabilization (for example, 2 to 9 stages), and the washing process can also be omitted. can.

■Specific Effects of the Invention According to the present invention, since the back layer of the silver halide photographic light-sensitive material contains a water-resistant quaternary onium compound, it can be used in the replenishment development process without raising the processing temperature. It becomes possible to reduce the amount of replenishment.

Furthermore, with a given developer, the amount of silver halide photographic material that can be processed is significantly increased compared to the conventional method.

Furthermore, it prevents low sensitivity and soft contrast.

The effect of stabilizing photographic properties can be obtained.

When processing with a small amount of developer, there is no need to provide a processing solution regenerating device in addition to the developing processor, so less space is required and costs can be reduced.

Furthermore, since the amount of replenishment is small, the amount of waste liquid is also extremely small, which helps solve environmental problems such as pollution.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in further detail.

<Example 1> Number average molecule i29.261 (measured by gel permeation chromatography), density 0.917 g/cm3.
500 KeV on a 200 μl thick polyethylene film
After crosslinking the polyethylene film by irradiating it with an electron beam of 45 megarads at a dose rate of 0.5 megarads/second in an electron beam ha speed chamber, methacrylic 1
%-2-N,N-dimethylaminoethyl and vinylbenzyl iodide at a molar ratio of 1.5 to impregnate the sample with the hepatumer. Next, this monomer-impregnated film was placed in a stainless steel container (the thickness of the stainless steel plate was 2 m/m), the air inside was replaced with nitrogen gas, the container was sealed, and the graft copolymerization was performed by irradiating ultraviolet rays. went.

This film was taken out, washed with 5% aqueous sulfuric acid to remove homopolymers, copolymers, etc. that do not undergo graft polymerization, and dried. The grafting rate of the graft membrane after drying was 45%, and the anion exchange capacity was 1.9111 eq/
g- A weakly basic film of dry resin film is formed.

On top of this IQ, a gelatin undercoat layer is applied (1.8g/
m″), then a blue-sensitive silver bromide emulsion layer containing a yellow coupler emulsion dispersion, a green-sensitive silver chlorobromide emulsion layer (silver chloride 70 mol %) containing a magenta coupler emulsion dispersion, and a cyan coupler emulsion dispersion. A color paper was prepared by coating a layer of a red-sensitive silver chlorobromide emulsion (70 mol % silver chloride) containing a substance and a gelatin layer containing an ultraviolet absorber.

As a coupler, α-(2,4-dioquine-5,5'-
dimethyloxazolidinyl)-α-piparoyl-2-chloro-5-((α-(2°4-di-t-amylphenoxy)butyramide))acetanilide, 1-(2,4,
6-Dolichlorophenyl)3-((2-chloro-3-tetradecanamido)anilino)-2-hirazo.

Ron-5-one and 2-((α-(2,4-di-t-amylphenoxy)-butanamide))-4,6-dichloro-5-methylphenol were used, respectively.

In addition, N, N”-G1 ((4
-hydroxy-6-anilino)-1゜3.5-triazin-2-yl)-4,4'-diaminostilbene-2,
Sodium 2'-disulfonate was used.

The color paper thus produced is referred to as P.

Experimental Example 1 A color paper Q was prepared by coating a silver halide emulsion similar to the above on a common RC support.

The coating amounts of coupler and silver salt for these color papers are as follows.

Red sensitive layer 0.4 0.5 Green sensitive layer
0.5 0.6 Seiraku Calendar 0.4
0.8 These color papers were exposed to light using a sensitometer (
After applying 500 CMS for 1 second, the fire was extinguished.

Processing process Temperature Time Development color development
Bleach-fixing at 33°C for 3 minutes and 30 seconds; Washing with water for 2 minutes. Next, color papers P and Q were each treated with a newly prepared color developing solution having the following composition.

f=L Benzyl alcohol Sodium 14-sulfite 2g Potassium bromide
0.5g sodium carbonate (monohydrate)
30g color developing agent *5g Hydroxylamine sulfur salt 2.5g Add water 11 wood 4-Amino-N-ethyl-N- (β-methanesulfonamide) - m-toluidine (sesquisulfate monohydrate) 1 Main 1j 1,000 sulfur ammonium 150 + all sodium sulfite 5gNa (FeI
Ir (EDTA)) 40gEDTA wood
Add 4g water
Color papers P and Q after the ethylenediaminetetraacetic acid melt treatment are referred to as strips P1 and Ql, respectively.

Color paper P and Q46rn', 20 each
Strips P2 and Q2 are the strips treated with the same color developing solution without replenishment and then treated with the solution.

The photographic properties (sensitivity, gradation, fog, etc.) of these strips were examined.

The results are shown in Table 1.

Table 1 Ql (Comparison) (Standard 1) PL (Invention) (Standard 2) From Table 1, in the conventional silver halide photographic light-sensitive material, exposed silver halide photographic light-sensitive materials can be processed with a developer without replenishment. As a result, the sensitivity and tone become lower, and desirable photographic properties cannot be obtained.1 However, the product of the present invention has little deterioration of photographic properties1, and even when processed with a developer without replenishment, it can produce a certain level of photographic performance. You can see that you can get sex.

Experimental Example 2> The above color papers P and Q were treated in the same manner as in Example 1.

However, the color developing solution used had the same composition as that shown in Example 1, but the silver halide photosensitive material 1trr'
For each process, a color developer replenisher having the composition shown below was replenished in the replenishment amounts shown in Table 2 below.

Color papers P and Q were processed.

Benzyl alcohol 18d Sodium sulfite 2.3g Sodium carbonate (1
water salt) 25g potassium hydroxide
3.3g color developing agent*7.
3g hydroxylamino sulfur salt Add 3.0g water 1 tree 4-amino-N
-Ethyl-N= (β-methanesulfonamide)-m-)luidine (sesquisulfate monohydrate) 20 under these conditions! ;per L, color paper P and Q
46 m'' were treated respectively. These are referred to as strips P3 and Q3.

The photographic properties obtained were almost the same as those of Pi and Ql.

Table 2 P3 (present invention) 110 Q3 (comparison) 350 From Table 2, when using the silver halide photosensitive material of the present invention,
It can be seen that the amount of replenishment fluid can be reduced to about 173 compared to the conventional one.

Even though the amount of replenishment is reduced, there is no need to raise the temperature of the processing solution, so the processing can be performed extremely stably.

This method can be said to be an excellent method that can reduce the amount of replenishment without requiring a regenerating device for the developer.

Procedure Yugin Seisho (Method) % Formula %? 1. Name of the invention Silver halide photosensitive material 3. Relationship with the person making the amendment Patent applicant address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 4. Agent 〒
101 Phone: 864-4498 Address: 4th floor, Chiyoda Iwamoto Building, 3-2-2 Iwakicho, Chiyoda-ku, Tokyo Name (8015) Patent attorney Minoru Watanabe,
Contents of the amendment (1) r J, Appl, Phot on page 2, line 2 from the bottom, page 3, line 2, and page 3, lines 6-7.

Eng, and J are respectively referred to as ``Journal of Abrant Photographic Engineering (J,
Appl, Phot, Eng,,) Corrected to J.

(2) rsMPTE on page 3, lines 1 and 3,
J and J are respectively corrected as ``SMPTE Journal (SMPTE, J,)J''.

(3) "rHunt" on page 3, line 14 of the same page is replaced with "Runt"
Hunt) Inc.”.

(4) r Co1 made by Hunt on page 3, lines 15-16
or Pr1nt Che+++1stries (P
Photographic Bulletin No. 49
) J to “Hunt production force 1 Razo l)
7to Chemistry (Golor PrintC
hemistries) (7 Odogura 74-/ri Pulten Number 49 (Photography
c Bulletin No., 49)) Correct with J.

(5) r P, Glafkid, page 18, lines 1-7
es'f; Chia+ie et Physi
que Photographique (Pau
1Monte1, 1967), G, F,
Photographic Emul by Duffin
sion Chemistry (The Fo
calPress, 1966), V, L,
Making and by Zelikman eta1
Coating Photographic Emau
l-sian (The Focal Press, 1
964)” is amended as follows.

Chim e Physique Photographic by P. Glafkides
ie et Physique Photograph
ique) [Paul Mant
el) Publishing, 1967)], G.F. Dufin (G.

F. Duffin) Photographic Emulge 7 Chemistry (Photographic
EmulsionChemistry) (The 7
2-The Focal Press
), 1966], V, L, Zelikman et al.
Author: Making and Coating Photography
E/ri emulsion, y(Making and C
oatingPhotographic Emarus
ion) (The 77?-Karpeles (The Fo
cal Press), 1964] (6) 18
Page 19 line to page 19 line 2 (7) r H, Fr1e
seri“Die GrundlagenderPho
tographischen Prozesse ff
1it SiLber-halogeniden”
(Akademische Verlagsgesel
l-scbaft, 1968) J is corrected as follows.

“Bar Freezer (H, Fr1eser)”
Prozesse Mitsutto Silver Halogenidene (Di)
e Grundlagen der Photogra
phi-schen Prozesse wi
tSilber-halogeniden)”
[Akadiminshe Verlags Gezersha 7t (
Akademische Verlagsgesell
schaft).

1968)J (7) rL, E on page 35, lines 11-14.

West, “Water Quality C
Photo.

Sci, andEng,, vol, 9 No, 6
Pages 344-359 (1965) J is corrected as follows.

``L,E, West'', ``Water Quality''
Quality Cr1teria) ” 7. #Tigerafu E/ri Science and Engineering (Photo.

Sci, and Eng,), Volume 9, Number 6
(val, 91b, 6) pages 344-359 (Page 3
44-359) (1965) J

Claims (1)

[Claims] A silver halide comprising at least one silver halide emulsion layer on one surface of a support, and a water-resistant quaternary onium compound present on the surface opposite to the surface on which the silver halide emulsion layer is formed. photosensitive material.