JPH0743514B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material containing a coating aid in a hydrophilic organic colloid coating layer, and in particular, unevenness in processing of a phenomenon, contamination of a processing solution and The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as a photographic light-sensitive material) that does not cause troubles due to contaminants (unevenness of drying, film stains due to adherence to transport rollers, etc.).

(Prior Art) As is well known, a photographic light-sensitive material is provided with several layers of hydrophilic colloid (usually gelatin) on a support such as a plastic film or paper. These layers have various functions such as an undercoat layer, an intermediate layer, a photosensitive layer and a protective layer, and each layer contains various inorganic or organic additives in order to satisfy those functions.

As described above, a general photographic light-sensitive material is formed from many hydrophilic organic colloid layers, and it is possible to apply these coating solutions in a thin layer uniformly and at high speed without coating failure such as cissing and uneven coating in the production thereof. Required. As a coating method, a continuous simultaneous multilayer coating method is often used in recent years.

The most difficult example of the coating process is the production of a color photographic light-sensitive material. In color photographic light-sensitive materials, color couplers,
Dissolving many water-insoluble additives such as UV absorbers and optical brighteners in high boiling organic solvents such as phthalate ester compounds and phosphate ester compounds to form an interface in hydrophilic organic colloids, especially gelatin solutions. It is used by dispersing it in the presence of a surfactant (so-called emulsified) and including it in the hydrophilic organic colloid layer. The use of a large amount of a surfactant as such an emulsifier makes it difficult to coat another hydrophilic organic colloid layer which is further coated on the hydrophilic organic colloid layer. When the amount of the emulsifier is reduced, the emulsified dispersion becomes unstable, causing aggregation and precipitation, and the photographic characteristics of the photographic light-sensitive material after coating become unstable.

Conventionally, various anionic surfactants have been used as coating aids for various coating solutions for photographic light-sensitive materials, and specific examples thereof are U.S. Pat.Nos. 2,240,476, 3,026,202 and 3,06.
8,101, 3,220,847, 3,415,649, West German patent 1,9
No. 42,665, etc.

(Problems to be Solved by the Invention) However, when an anionic surfactant is used as a coating aid to further coat a colloidal solution such as gelatin on a colloidal layer such as gelatin, it is contained in gelatin. Since the solubility of the anionic surfactant is extremely reduced due to the alkaline earth metal ion such as calcium, when the anionic surfactant is added to the gelatin coating solution, it precipitates as a hydrated solid substance. There was a drawback that the coatability was significantly deteriorated.

Also, U.S. Pat. No. 3,850,642 used for antistatic,
A cationic antistatic agent such as a cationic surfactant disclosed in JP-A-57-146248 or the like, or a cationic polymer disclosed in JP-A-55-7763 or JP-A-54-18728,
When these anionic surfactants as coating aids are used together in the same light-sensitive material, if they are added to the same coating solution, insoluble (or hardly soluble) complex is formed between them and cissing occurs. There was a serious drawback that it would end up. On the other hand, even if both are added to different layers, they are dissolved in the processing solution when the photosensitive material is subjected to development processing, and both form an insoluble complex in the processing solution, resulting in uneven processing and development stain. There was a problem.

In recent years, it has been suggested to reduce the amount of rinsing water at the time of treatment from the viewpoint of environmental protection, water quality, cost, or simple and compact treatment equipment.

Further, a method of reducing the amount of treatment liquid by using a liquid to which various chemicals are added instead of a mere washing step with water (for example, JP-A-57-8542, JP-A-58-14834, JP-A-57-132146, and JP-A-57-132146). -186
No. 31, No. 59-184345, No. 57-197540, No. 58-134636
No.) As described above, when the amount of washing water is reduced or a chemical is used, the surfactant flowing out from the photographic light-sensitive material remains unevenly on the surface of the coating film and discolors with time, or when it is dispersed in the coating film. It is known that a so-called sweating phenomenon, which is caused by aggregation and coalescence of a boiling solvent, a coupler, etc., is promoted.

Further, in recent years, attempts have been made to reduce the amount of replenishing treatment liquid from the viewpoint of cost, but in this case as well, the ratio of the surfactant accumulated in the treatment liquid increases, and the anionic surface active agents disclosed so far are disclosed. The problem was the formation of tar-like insolubles when the photosensitizing agent was continuously processed.

Attempts have been made to thicken the treatment liquid in order to further shorten the treatment time, but again, the same problems as described above were encountered.

As a part of shortening and simplifying the processing time, a bleaching accelerator is added to the bleaching or bleach-fixing solution (JP-A-53-95630 and JP-A-57-19295).
No. 3, Japanese Patent Publication No. 54-12056, and US Pat. No. 4,552,834) are known.

However, it was found that an insoluble complex was formed between these bleaching accelerator and the anionic surfactant flowing out from the photosensitizer to cause contamination of the processing solution, and its improvement was desired.

On the other hand, recently, JP-A-60-76741 has been disclosed as a method for preventing contamination of a treatment liquid of an ethylene oxide nonionic surfactant used as an antistatic agent. The patent describes that anionic surfactants containing ethylene oxide groups in the molecule are effective. Certainly, this compound improves the treatment stain by the complex with the cationic compound and the treatment liquid stain of the ethylene oxide nonionic surfactant used together, as compared with the above-mentioned anionic surfactant.
However, it is not sufficient that any processing liquid does not cause processing contamination. For example, as mentioned above, in recent years, due to environmental protection, cost reduction, or simple and compact processing equipment, the processing solution is becoming thicker, the amount of replenishing processing solution is being reduced, and the processing solution is being rapidly processed. pollution,
The problem of stains on the photosensitive material due to adherence of contaminants to the transport roller has not been solved.

As described above, the occurrence of these problems may be caused by the properties of the surfactant itself used for each purpose or by the interaction with other coexisting additives.

Therefore, in order to solve these problems, it is considered most preferable to improve the individual surfactants used for each purpose, but in reality, it may impair the intended performance. There are many significant difficulties.

(Object of the Invention) A first object of the present invention is to apply a gelatin-containing solution or other hydrophilic colloid solution uniformly on a support such as film or paper or other photographic layer without cissing. To provide a photographic light-sensitive material.

A second object of the present invention is, without impairing the antistatic property,
An object of the present invention is to provide a photographic light-sensitive material which does not cause contamination of a developing solution and has no image unevenness.

(Means for Solving the Problems) These objects of the present invention are achieved by incorporating a compound represented by the following general formula [I] into a silver halide emulsion layer or another hydrophilic colloid layer. It was

General formula [I] A-X-YB SO₃In the formula M, A is an alkyl group having 8 to 25 carbon atoms, an alkenyl group,
Represents an aryl group, X is -O-, And R is an alkyl group or Y-B. Y is small
KutoUnit is included, a is 0 to 50, preferably
Is 0 to 20, b is 1 to 50, preferably 1 to 20
It

B represents a divalent linking group (provided that The group is excluded. ) N represents 0 or 1.

M represents a cation.

Further, an alkyl group, an alkenyl group of A in the general formula [I],
The aryl group may be further substituted.

Preferred examples of A include C ₁₂ H ₂₅ −, C ₁₆ H ₃₃ −, C
₁₈ H ₃₅ −, C ₁₁ H ₂₃ CO, C ₁₁ H ₂₃ CONHCH ₂ CH ₂ −, Etc.

As a specific example of Y, Etc.

Specific examples of B include an alkylene group having 2 to 10 carbon atoms, a carbonylalkylene group, and the like, for example, —CO ₂ —CH ₂ —, CH _2
4 , Etc.

Specific examples of M include alkali metals, alkaline earth metals,
Examples thereof include ammonium and the like, such as Na, K, Mg, NH ₄ , N (CH ₃ ) ₄ .

Next, specific examples of the compound used in the present invention will be shown, but the invention is not limited thereto.

The compounds represented by the general formula [I] are characterized by having a glycidol group in the molecule.

It is considered that the reason why the compound of the present invention does not contaminate the treatment solution is that the solubility of the compound in the treatment solution having a high ionic strength is remarkably improved by having the glycidol group.

Today, as mentioned above, the problem of processing solution contamination is becoming more serious as the composition of processing solutions changes, but various photographic additives, especially those with a structure like a surfactant, are processed by the film. Nucleic acid is contained in the solution, which causes contamination of the processing solution. For example, an ethylene oxide nonionic surfactant used as an antistatic agent is liable to contaminate the treatment liquid, but it is also possible to prevent the contamination of the treatment liquid by using the compound of the present invention together. Further, the compound of the present invention is remarkably excellent in the wettability of the photographic processing liquid to the photographic light-sensitive material and does not cause image unevenness. For example, when it is used as a reversal color photosensitive material, the wettability of the reversal bath (containing Sn ⁺⁺ ) can be improved.

The compound represented by the general formula [I] used in the present invention can be synthesized by a general method.

Synthesis Example (Synthesis of Compound Example 1) Dry in a 300 ml flask equipped with an agitator, reflux condenser, thermometer, and dropping funnel. OP-3, Nikko Chemicals Co., Ltd. 67.7g (0.2mol) and NaOH
Add 2.8g and heat to 155-160 ℃ and stir. Inner temperature 155
Glycidol 44.4 g (0.6 mol) is added dropwise over 1.5 ^hrs while maintaining at ~ 160 ° C. After dropping, stir and react at 160 ° C for 7 ^hrs . Unreacted glycidyl is not observed at all. After cooling, add 200 ml of ethanol to dissolve and neutralize with conc-HCl. After distilling off the solvent under reduced pressure, chloroform 250 m
Add l and let stand overnight. The by-produced polyglycerin comes out as an insoluble matter. The insoluble material was removed by suction filtration using Celite and the solvent was distilled off under reduced pressure to obtain a pale yellow viscous liquid (145 g). From IR and NMR, the number of moles of glycidol added is 2.5.
It was. (However, 1 part of the reaction product with the secondary OH group is also included in the reaction of the glycidol group.) (2) Synthesis of compound 1 In a 300 ml flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel. , Synthesized in (1) above 99.4g (0.19mol) and 32ml of toluene are stirred and dissolved. Add 9.9 g of NaOH and add 33.63 g (0.247 mol) of butane sultone over 30 minutes while stirring at 50 ° C. After completion of dropping, the mixture is stirred for 30 minutes at the same temperature and stirred at 70 to 75 ° C for 4 ^{hrs to} react.

Next, 500 ml of ethanol and 400 ml of methanol were added, insoluble matter was filtered off, evaporated under reduced pressure, reprecipitated from acetonitrile, dried under reduced pressure,
A wax-like object is obtained.

In the present invention, the compound represented by the general formula [I] can be added to the hydrophilic organic colloid and used as a coating aid.

The amount added to the photographic light-sensitive material per square meter
The amount is 0.001 to 2 g, preferably 0.003 to 0.5 g, and particularly preferably 0.004 to 0.2 g.

As a method of adding the compound to the coating solution, the compound represented by the general formula [I] may be added as it is, or may be added by dissolving it in water, methanol, an organic solvent or a mixed solution thereof.

The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (eg silver nitrate) solution and a water-soluble halogen salt (eg potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. able to make. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of silver halide (in the case of spherical grains or grains close to spheres, grain diameter, in the case of cubic grains, grain size is represented by average grain size based on projected area) is preferably 2 μ or less. , Especially preferred
It is 0.8 μ or less. The particle size distribution may be narrow or wide.

The shape of these silver halide grains may be cubic, octahedral, mixed crystal thereof, or tabular as described in JP-A Nos. 58-127921 and 58-113926.

Further, two or more kinds of silver halide photographic emulsions formed separately may be mixed. Further, even though the crystal structure of the silver halide grains is uniform to the inside, it has a layered structure in which the inside and the outside are of a progressive structure, and it is described in British Patent 635,841 and U.S. Patent 3,622,318. Such a so-called conversion type may be used. Further, it may be of a type in which a latent image is mainly formed on the surface or an internal latent image type of which a latent image is formed inside the particles.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may coexist.

As the silver halide emulsion, a so-called unripened emulsion (primitive emulsion) which is not chemically sensitized can be used, but it is usually chemically sensitized. For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate, thioureas, mercapto compounds, rhodanins), a reducing substance (for example, Reduction sensitization using tin salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, noble metal compounds (eg, gold compounds, complex salts of Group VIII metals such as platinum, iridium, palladium, etc.) ), Or the like, can be used alone or in combination.

As the binder or protective colloid that can be used in the emulsion layer and intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, 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; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate, dextran and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As the gelatin, acid-treated gelatin or enzyme-treated gelatin may be used in addition to lime-treated gelatin, and a hydrolyzed product or an enzymatically-decomposed product of gelatin may also be used.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chromium salts (chromium deuterium, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-). Triazine, etc.), mucohalogen acids (mucochromic acid, mucophenoxycyclo acid, etc.), N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio))
Methane sulfonate, etc.) and haloamidinium salts (1
-(1-chloro-1-pyridylmethylene) pyrrolidinium-2-naphthalene sulfonate) and the like can be used alone or in combination.

Among these compounds, active vinyl compounds or active halogen compounds can be preferably used.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example,
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Non-ionic substances such as all-alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglycerides, alkyl phenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants; alkyl carboxylates, alkyl sulphonates, alkyl benzene sulphates Acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene A carboxy group, such as alkyl phosphates,
Anionic surfactants containing an acidic group such as a sulfo group, a phospho group, a sulfate ester group, and a phosphate ester group; amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkylbetaines, amine oxides; heterocyclic quaternary ammonium salts such as alkylamine salts, pyridinium and imidazolium, and aliphatic or Cationic surfactants such as phosphonium or sulfonium salts containing heterocycles can be used.

Fluorine-containing surfactants are particularly effective as antistatic agents, and can be used as anions, cations, betaines and nonions.

Preferred examples of the compound will be described below.

F-1 C₇F₁₅COOH F-2 C₈F₁₇SO₃K F-10 C₈F₁₇CH₂OCH₂CH₂O H n: 12 The amount of the fluorine-containing compound according to the present invention added to the photographic constituent layers is
The photo-constituting layer 1m²Per 0.1mg ~ 1g is preferred, 0.5mg ~ 50
0 mg is particularly preferred.

They are also applied for coating aids, lubrication, defoaming, emulsion dispersion, sensitization and other improvement of photographic properties.

Further, in the present invention, a lubricating composition, for example, US Pat.
Modified silicones such as those shown in 3,079,837, 3,080,317, 3,545,970, 3,294,537 and Japanese Laid-Open Patent Publication No. 52-129520 may be contained in the photographic constituent layers.

In the present invention, inorganic or organic fine particles (so-called matting agent) may be used in the photographic light-sensitive material for the purpose of improving antistatic property and adhesiveness. These are Belgian Patent No. 6554
No. 24, JP-A No. 51-6017, No. 53-7231, No. 62-89957,
It is described in Japanese Patent Application Nos. 61-21901 and 62-50684, for example, barium sulfate, strontium carbonate, silicon dioxide, polymethyl (meth) acrylate, methyl (meth).
Acrylate / (meth) acrylic acid copolymers, fluorine-containing polymer dispersions, silicon-containing polymer dispersions, ethyl acrylate / styrene sulfonic acid sodium salt copolymers, or alternatively, JP-A-62-11251. The matting agent having the fixed hydrophilicity described above, and further a matting agent containing a group capable of crosslinking with a binder such as gelatin (eg, glycidyl, vinylsulfonyl, isocyanate, etc.) can be mentioned.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include
Cyanine dye, merocyanine dye, complex cyanine dye,
Included are complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
It is a dye belonging to a merocyanine dye and a composite merocyanine dye. To these dyes, the nucleus shift normally used for cyanine dyes as a basic heterocyclic nucleus can also be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon rings fused to nuclei of indolenin, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benzimidazole nuclei A nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiovidandoin nucleus, 2-thiooxazolidine-2, as a nucleus having a ketomethylene structure.
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied. Although these sensitizing dyes may be simply used, combinations thereof may be used, and the combination of sensitizing dyes is often used particularly for the purpose of strongly dyeing.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary ammonium salt. Compound, urethane derivative,
It may contain a urea derivative, an imidazole derivative, 3-pyrazolidones and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer (so-called latex) in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability. . For example, alkyl (meth) acrylate, glycidyl (meth) acrylate, styrene or the like alone or in combination, or a polymer containing a combination of these with acrylic acid, methacrylic acid or the like as a monomer component, and an aqueous dispersion thereof are used. it can. Further, for these dispersions, the fluorine-containing or silicon-containing latex described in JP-A-62-17745 can be used. JP 62
It is also possible to use a latex having a hydrophilic group fixed therein described in JP-A-11251 or a latex having an anion group / hydration layer forming group described in Japanese Patent Application No. 61-195788.

The light-sensitive material prepared by using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic emulsion used in the present invention, various compounds other than the compound of the present invention may be used in combination for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can That is, azoles {eg benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds {eg mercapto Thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptotetrazole), mercaptopyrimidines, mercaptotriazines and the like}; thioketo compounds such as oxadrinethione; azaindenes {eg triazaindenes, tetraazaindenes, ventaazaindenes and the like}; benzenethiosulfonic acid Many compounds known as antifoggants or stabilizers, such as benzene sulphonic acid, benzene sulphonic acid amide, etc. can be added.

The photographic light-sensitive material of the present invention is a color image-forming coupler, that is, a compound capable of forming a color by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in color development processing. May be included. The coupler is preferably a non-diffusing coupler having a hydrophobic group called a ballast group in the molecule, or a polymerized coupler. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions. Further, a colored coupler having a color correction effect, or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be included. The product of the coupling reaction may be colorless and may also contain a colorless DIR coupling compound which releases a development inhibitor.

Examples of the yellow coupler include, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020,
Those described in No. 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,
No. 619, No. 4,351,897, European Patent No. 73,636, US Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
Issue, Research Disclosure No. 24230 (6 June 1984)
JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferable.

Examples of cyan couplers include phenol and naphthol phenols, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,146,396.
No. 4,228,233, No. 4,296,200, No. 2,369,929
No. 2, No. 2,801,171, No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,308, No. 4,334,0
No. 11, 4,327,173, West German Patent Publication No. 3,329,729,
European Patent 121,365A, U.S. Patent 3,446,622, and
Those described in 4,333,999, 4,451,559, 4,427,767, etc. are preferable.

Colored couplers to correct unwanted absorption of colored dyes are VII-G of Research Disclosure No.17643.
Section, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, and British Patent 1,14.
Those described in 6,368 are preferable.

As the coupler in which the color forming dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is RD17643, the patents described in the paragraph VII-F, JP-A-57-154234 and JP-A-60-184248,
61-249052, 61-238057, 61-236550, 61-
240240, 61-231553, 61-233741, U.S. Patent No.
Those described in 4,248,962, 4,477,563 and 4,146,396 are preferable.

Examples of couplers that release an image-like nucleating agent or a development accelerator during development include British Patent Nos. 2,097,140 and 2,13.
Those described in 1,188, JP-A-59-157538 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP-A-60-18
DIR redox compound releasing coupler described in No. 5950,
Examples thereof include couplers that release a dye that restores color after separation described in EP 173,302A.

In addition to the DIR-coupler, a compound releasing a development inhibitor upon development may be contained in the light-sensitive material. Examples of these include, for example, U.S. Patents 3,379,529 and 3,62.
0,746, JP-A-60-233648, 61-18946, 61-230
Those described in No. 135 and the like are preferable.

The above couplers and the like can be used in combination in two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound in two or more different layers.

To introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 are used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphonate, triphenyl phosphonate, tricresyl phosphonate, dioctyl butyl phosphonate), citric acid ester (eg acetyl) Tributyl citrate), benzoic acid esters (eg octyl benzoate), alkylamides (eg cyethyllaurylamide), fatty acid esters (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate) )
Or an organic solvent having a boiling point of 30 ° C. to 150 ° C., for example, a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
After being dissolved in methyl cellosolve acetate or the like, it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Also, Japanese Patent Publication No. 48-30494, Japanese Patent Publication No. 51-39853, and Japanese Patent Publication No. 50-1.
02334, JP-A-51-25133, JP-A-51-59943, Japanese Patent Application No. 61-162813, Japanese Patent Application No. 61-187996, Japanese Patent Application No. 61-189771.
West Germany Patent No. 2,830,917, U.S. Patent No. 3,619,195
It is also possible to use a dispersion method using a polymer described in the above publication.

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.

A known anti-fading agent can be used in the photographic light-sensitive material of the present invention. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols.

The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used depending on the purpose.

These additives are described in more detail in Research Disclosure No. 17643 (December 1978) and No. 18716 (1979).
(November, 2013), and the relevant parts are summarized in the table below.

For the light-sensitive material of the present invention, various known quaternary ammonium salt (or phosphonium salt) polymers can be used as the polymers that provide cation sites in the fixing solution. The quaternary ammonium salt (or phosphonium salt) polymer is widely known as a mordant polymer or an antistatic polymer in the following publications.

JP 59-166,940, U.S. Patent 3,958,995, JP 55-14
2339, JP-A-54-126,027, JP-A-54-155,835, JP-A-53
-30328, water-dispersed latex described in JP-A-54-92274; US Patents 2,548,564, 3,148,061, and 3,756,814.
Polyvinylpyridinium salt described in US Pat. No. 3,709,69
Water-soluble quaternary ammonium salt polymer described in 0; water-insoluble quaternary ammonium salt polymer described in U.S. Pat. No. 3,898,088, and JP-A-49-13925, JP-B-49-15820, U.S. Patents 2,882,156, and 2,747,228. Polymers containing a residue formed by the reaction of the ketone with the aminoguanidine derivative described in 1. can be used.

Preferred polymers are listed below.

Compound example The amount of the polymer that provides cation sites in the fixing solution is 0.1 or more, preferably 0.3 to 100, and more preferably 0.5 to 30, as a unit of cation sites per 1 mol of the total iodine in the light-sensitive material.

The polymer providing a cation site can be added to the light-sensitive layer or the non-light-sensitive layer, but it is preferable to add a non-light-sensitive layer between the light-sensitive layer and the support. It is particularly preferable when the additive layer is an undercoat layer. Among the polymers that provide cation sites, those that have a high ability to capture halogen ions are preferable.

The polymer which provides a cationic site that can be contained in the light-sensitive material of the present invention can also be used as a substance which mordantes an anti-halation or anti-irradiation dye. In this case, it is preferable to use an anionic dye that is decolorized in the developing-fixing-water washing process. Further, in a double-sided X-ray film for direct medical treatment, it is possible to cut the crossover light and improve the sharpness by mordanting a decolorizing dye on the lower side of the emulsion layer. The addition of the cation site-providing polymer and the anionic dye produces particularly preferable effects.

Hereinafter, preferable dyes that can be used in the light-sensitive material of the present invention will be described.

Such dyes include, for example, British Patent Nos. 506,385 and 1,1.
77,429, 1,131,884, 1,338,799, 1,385,37
No. 1, 1,467,214, 1,433,102, 1,553,516,
JP-A-48-85,130, JP-A-49-114,420, JP-A-52-117,123
No. 55, 161, 233, 59, 111, 640, Japanese Patent Publication No. 39-22, 06
9, 43-13,168, U.S. Pat.
Oxonol dyes having a pyrazolone nucleus and a barbituric acid nucleus described in 9,985 and 4,078,933, U.S. Pat.Nos. 2,533,472, 3,379,533, and British Patent 1,278,621.
Other oxonol dyes described in UK patent No.
575,691, 680,631, 599,623, 786,907,
No. 907,125, No. 1,045,609, U.S. Pat.No. 4,255,326
Azo dyes described in JP-A-59-211,043, JP-A-50-100,116, JP-A-54-118,247, British Patent No. 2,014,59
No. 8, azomethine dyes described in the same 750,031, etc., anthraquinone dyes described in British Patent No. 2,865,752,
U.S. Patent Nos. 2,538,009, 2,688,541, 2,538,008
No., British Patent Nos. 584,609 and 1,210,252, JP-A-50-4
0,625, 51-3,623, 51-10,927, 54-118,247
Arylidene dyes described in JP-B Nos. 48-3,286 and 59-37,303, and JP-Bs 28-3,082 and 44-16,594
No. 59-28,898 and the like styryl dyes described, British Patent No. 446,583, the same 1,335,422, triarylmethane dyes described in JP-A-59-228,250, etc., British Patent No. 1,
075,653, 1,153,341, 1,284,730, 1,475,2
28, 1,542,807 and the like, merocyanine dyes, and British Patent Nos. 2,843,486, 3,294,539, and the cyanine dyes.

Representative dyes are shown below, but the present invention is not limited thereto.

Various exposing means can be used for the light-sensitive material of the present invention. Any light source that emits a broad radiation corresponding to the sensitivity wavelength of the light-sensitive material can be used as an illumination light source or a writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen atom-sealed lamps, mercury lamps, fluorescent lamps and strobes or metal burning flash bulbs are common. A gas, a dye solution or a semiconductor laser, a light emitting diode, or a plasma light source which emits light in a wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, a linear line is formed in a micro-scatter array using a phosphor screen (CRT, etc.) emitted from a phosphor excited by an electron beam, liquid crystal (LCD), lanthanum-doped lead titan zirconate (PLZT), etc. Alternatively, an exposure means combining a planar light source can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

For the photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. The treatment temperature is usually selected from 18 ° C to 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, either a phenomenon process for forming a silver image (black and white photographic process) or a color photographic process including a developing process for forming a dye image can be applied.

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

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-
Amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfoamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used.

If necessary, any development accelerator can be added to the color developing solution. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation and fog prevention. Here, "substantially free of benzyl alcohol" means that the amount of benzyl alcohol per color developer is 2 ml or less. Preferably, it contains no benzyl alcohol.

Further, in the color developing solution, other preservatives such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and the like, and a carbonyl sulfite adduct are added as necessary. It can be added. The amount of these additives to be added to the color developing solution is 0 g to 20 g / l, preferably 0 g to 5 g / l, and a smaller amount is preferable if the color developing solution can be maintained. In order to improve the color developability, it is preferable that the sulfite ion is not substantially contained, and more specifically, it is 0.5 g / l or less, more preferably 0.2 g / l or less in terms of sodium sulfite.

In addition, LFA Messon's "Photographic Processing Chemistry", published by Focal Press (1966)
226-229, U.S. Pat.Nos. 2,193,015 and 2,592,364
Nos. 4,483,933, and JP-A-48-64933 may be used.

The developer may be a development inhibitor such as a pH buffer such as an alkali metal sulfite, a carbonate, a borate and a phosphate, a bromide, an iodide or an organic antifoggant other than the compound of the present invention, or a fog. Inhibitors and the like can be included. If necessary, a water softener, a preservative such as hydroxylamine, an organic solution such as benzyl alcohol or diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as amines, a dye-forming coupler, a competitive coupler, Fogging agent such as sodium boron hydride, auxiliary developing agent such as 1-phenyl-3-pyrazolidone, viscous additive, polycarboxylic acid type chelating agent described in U.S. Pat. No. 4,083,723, West German publication (OLS) 2,62
The antioxidant described in No. 2,950 may be included.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like are used. For example, an organic complex salt of ferricyanide, dichromate, iron (III) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or a quenching agent. Complex salts of organic acids such as acids, tartaric acid and malic acid; persulfates, permanganates, nitrosphenol and the like can be used. Of these, potassium ferrocyanide, sodium iron (III) ethylenediaminetetraacetate and ammonium iron (III) ethylenediaminetetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

For bleaching or bleach-fixing solutions, U.S. Pat.
Various additives can be added in addition to the bleaching accelerators described in 3,241,966, JP-B-45-8506, JP-B-45-8836, and the thiol compounds described in JP-A-53-65732.

The washing process may be carried out in one tank, but in most cases it is 2
It is carried out by a multi-stage countercurrent washing method of more than a tank. The amount of water in the washing step can be arbitrarily set according to the type and purpose of the color light-sensitive material. For example, Journal of the Motion Picture and Television Engineering 64: 248-253 (1955 (May issue) “Water Florents in Immersion Watering of Motion Picture Film” (Water Flow Rat)
es in Immersion-Washing of Motion Picture Film, S.
R. Goldwasser).

When reducing the amount of water to be washed, the occurrence of bacteria and mold becomes a problem, but as a reaction therefor, washing water with reduced calcium and magnesium described in Japanese Patent Application No. 61-131632, a bactericidal agent and an antibacterial agent. , For example, the Journal of
Antibacterial and Anfunningal Agents (J.Antibact.Antifug.Agents) vol.11, No.5, p
207 to 223 (1983) and compounds described in Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Chemistry") can be added. Further, as a water softener, ethylenediaminetetraacetic acid, various hardeners or the like can be added as required. Or by West Photographic
Science and Engineering Magazine (Phot.Sci.E
ng.), Vol. 6, pp. 344-359 (1965), etc., may be added. It is particularly effective to add a chelating agent or a bactericide / antifungal agent.

The water washing step is performed by multi-stage countercurrent water washing of two or more tanks (for example, 2-9
It is also possible to reduce the amount of washing water by using a tank). Further, instead of the water washing step, a multistage countercurrent water washing treatment step as described in JP-A-57-8543 may be carried out. Various compounds are added to the washing bath for the purpose of stabilizing the image. For example, various buffers (eg borate, metaborate, borax, phosphate, carbonate, etc.) for adjusting the membrane pH (eg pH 3-9).
Typical examples include aldehydes such as potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. Other chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (thiazole-based, isothiazole-based, halogenated phenol, sulfanilamide, benzo) Various additives such as triazole), optical brighteners and hardeners may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment in order to improve the image storability.

Immediately after the washing step, a stabilizing bath containing a draining agent and formalin can be used. When processing a light-sensitive material using a 2-equivalent magenta coupler, the formalin may be removed or the stabilizing bath itself may not be used.

The washing time of the light-sensitive material of the present invention varies depending on the processing conditions, but is usually 20 seconds to 10 minutes, and preferably 20 seconds to 5 minutes.

(Examples) Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 On a subbed cellulose triacetate film support,
A multi-layer color light-sensitive material having the following composition was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

1st layer (anti-halation layer) Black-white colloidal silver …… 0.5 Gelatin …… 1.3 Colored coupler C-1 …… 0.06 UV absorber UV-1 …… 0.1 Same as above UV-2 …… 0.2 Dispersion oil Oil-1 …… 0.01 Same as above Oil-2 …… 0.01 Desilvering accelerator BA-1 …… 0.03 Surfactant SA-2 …… 0.01 Second layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ) …… 0.15 Gelatin …… 1.0 Colored coupler C-2 …… 0.02 Dispersion oil Oil-1 …… 0.1 Surfactant SA-2 …… 0.01 Hardener H-2 …… 0.2 Third layer (first red-sensitive emulsion layer) Silver iodobromide Emulsion (silver iodide 2 mol%, average grain size 0.3μ)
Silver 0.4 Gelatin …… 0.6 Sensitizing dye I …… 1.0 × 10 ^-4 Sensitizing dye II ・ ・ ・ 3.0 × 10 ^-4 Sensitizing dye III …… 1 × 10 ^-4 Coupler C-3 …… 0.06 Coupler C-4 …… 0.06 Coupler C-8 …… 0.04 Coupler C-2 …… 0.03 Dispersion oil Oil-1 …… 0.03 Same as above Oil-3 …… 0.012 Surfactant SA-1 …… 0.02 4th layer (second red emulsion) Layer) Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.5 μ)
0.7 Gelatin ...... 2.5 Sensitizing dye I ...... 1.0 × 10 ^-4 Sensitizing dye II ・ ・ ・ 3 × 10 ^-4 Sensitizing dye III ・ ・ ・ 1 × 10 ^-4 Coupler C-3 ・ ・ ・ 0.24 Coupler C-4 ・ ・ ・... 0.24 Coupler C-8 ... 0.04 Coupler C-2 ... 0.04 Dispersion oil Oil-1 ... 0.15 Same as above Oil-3 ... 0.02 Surfactant SA-1 ... 0.05 Fifth layer (third red-sensitive emulsion layer) ) Silver iodobromide emulsion (silver iodide 1.0 mol%, average grain size 0.7 μ) ...
Silver 1.0 Gelatin …… 1.0 Sensitizing dye I …… 1 × 10 ^-4 Sensitizing dye II …… 3 × 10 ^-4 Sensitizing dye III …… 1 × 10 ^-4 Coupler C-6 …… 0.05 Coupler C-7 …… 0.1 Dispersed oil Oil-1 …… 0.01 Same as above Oil-2 …… 0.05 Surfactant SA-1 …… 0.01 6th layer (intermediate layer) Gelatin …… 1.0 Compound Cpd-A …… 0.03 Dispersed oil Oil-1 …… 0.05 Surfactant SA-2 …… 0.02 Polylatex (polymer of methylmethacrylate / acrylic acid = 95: 9 (molecular weight about 100,000) is polyvinyl alcohol (5% by weight of molecular weight about 150,000 polymer). Dispersed together with gelatin aqueous solution) ........ 0.3 Seventh layer (first green sensitive emulsion layer) Silver iodobromide emulsion (4 mol% silver iodide, average grain size 0.3 .mu.) ....
0.30 Sensitizing dye IV …… 5 × 10 ^-4 Sensitizing dye VI …… 0.3 × 10 ^-4 Sensitizing dye V …… 2 × 10 ^-4 Gelatin …… 1.0 Coupler C-9 …… 0.28 Coupler C-5… 0.03 Dispersed oil Oil-1 ... 0.5 Surfactant SA-1 ... 0.04 Eighth layer (second green emulsion layer) Silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.5 µ) ... …
0.4 Gelatin ...... 0.8 Sensitizing dye IV ・ ・ ・ 5 × 10 ^-4 Sensitizing dye V ・ ・ ・ 2 × 10 ^-4 Sensitizing dye VI ・ ・ ・ 0.3 × 10 ^-4 Coupler C-9 ・ ・ ・ 0.25 Coupler C-1 ・ ・ ・… 0.03 Coupler C-10 …… 0.015 Coupler C-5 …… 0.01 Dispersion oil Oil-1 …… 0.2 Surfactant SA-1 …… 0.01 9th layer (3rd green emulsion layer) Silver iodobromide emulsion ( 6 mol% silver iodide, average grain size 0.7μ)
Silver 0.85 Gelatin …… 1.0 Sensitizing dye VII …… 3.5 × 10 ^-4 Sensitizing dye VIII …… 1.4 × 10 ^-4 Coupler C-11 …… 0.01 Coupler C-12 …… 0.03 Coupler C-13 …… 0.24 Coupler C-1 ...... 0.02 Coupler C-15 ...... 0.02 Dispersion oil Oil-1 ...... 0.24 Same as above Oil-2 ...... 0.05 Surfactant SA-1 ...... 0.03 10th layer (yellow filter layer) Gelatin ...... 1.2 Yellow Colloidal silver …… 0.08 Compound Cpd-B …… 0.1 Dispersion oil Oil-1 …… 0.3 Surfactant SA-2 …… 0.04 11th layer (1st blue emulsion layer) Monodispersed silver iodobromide emulsion (iodination) Silver 4 mol%, average particle size 0.3
μ) Silver 0.4 Gelatin …… 1.0 Sensitizing dye IX …… 2 × 10 ^-4 Coupler C-14 …… 0.9 Coupler C-5 …… 0.07 Dispersion oil Oil-1 …… 0.2 Surfactant SA-1 …… … 0.04 12th layer (2nd blue emulsion layer) Silver iodobromide (10 mol% silver iodide, average grain size 1.5μ) …… Silver 0.5
Gelatin: 0.6 Sensitizing dye IX: 1 × 10 ^-4 Coupler C-14: 0.25 Dispersion oil Oil-1: 0.07 Surfactant SA-1: 0.03 13th layer (1st protective layer) Gelatin: 0.8 UV absorber UV-1 0.1 Same as UV-2 …… 0.2 Dispersion oil Oil-1 …… 0.01 Dispersion oil Oil-2 …… 0.01 Surfactant SA-1 …… 0.04 14th layer (2nd protection layer) Fine grain silver bromide (average particle size 0.07μ) …… 0.5 gelatin …… 0.45 Poly (methylmethacrylate-perfluorooctylethylacrylate-acrylic acid (70:20:10) particles (diameter 1.5μ) …… 0.2 Hard film Agent H-1: 0.4 Formaldehyde scavenger S-1: 0.5 Formaldehyde scavenger S-2: 0.5 Surfactant SA-4 The addition amount is as shown in Table 2.

SA-5 〃 Antistatic agent SA-6 〃 (Back layer coating liquid) Acetone / methanol solution containing diacetyl cellulose colloidal silica and the following compounds was used as the first layer coating liquid, and a methanol liquid containing diacetyl cellulose on it Was used as the coating liquid for the second layer.

Then, one side of the support base was sequentially coated with the coating solution for emulsion layer, and the other side was coated with the coating solution for back layer to prepare a sample.

Also, the surfactants of the 14th layer were changed to the samples 101 to 105 as shown in Table 2 below.

Next, the chemical structural formulas or chemical names of the compounds used in this example are shown below.

Oil-1 Tricresyl phosphate Oil-1 Dibutyl phthalate Oil-3 Bis (2-ethylhexyl) phthalate The sample produced as described above was designated as A.

SA-3 CH ₃ (CH ₂ ) ₁₀ CH) = CHCH ₂ SO ₃ Na SA-6 C ₈ F ₁₇ SO ₂ O (C ₃ H ₇ ) CH ₂ COOK The photographic element was then exposed to 25 CMS with a tungsten light source adjusted to a color temperature of 4800 ° K with a filter before being subjected to the following processing with an automatic processor.

In the above treatment step, the washing with water was a countercurrent washing method from to.

<Washing liquid> Normal water was used.

First, the exposed color light-sensitive material (35 m / m width) was continuously processed by 20 m per day for 20 days using an automatic processor having a tank capacity shown in Table 1 to obtain a sample.

Also, as the washing with water in Table 1, the following washing solution was used and the treatment was continued for 20 days in the same manner as in Table 1 except that the replenishing amount was changed to 27 ml. A sample was obtained.

The following tests were conducted on each of the samples thus obtained before and after the development treatment.

(B) Coatability The number of repellents per square meter of the sample before the treatment was examined. The larger the number of repellants, the poorer the coating property.

(B) Static mark After conditioning the sample before treatment for 3 hours at 25 ° C and 10% relative humidity, under the same conditions between nylon and urethane rollers (diameter 2.5 cm, roller pressure 0.5 kg per 1 cm film) Through The sample was processed according to the above-mentioned processing method, and the static marks seen on the image were judged according to the following criteria.

A: No static marks are seen.

B: There was a slight 〃.

C: There was a lot of 〃.

D: 〃 was seen all over.

(C) Treatment unevenness The samples obtained by the treatment were evaluated in the following four stages.

A: No uneven density is observed.

B: 〃 Somewhat acceptable.

C: 〃 Equivalent 〃 D: 〃 Remarkably 〃 (D) The sample obtained by the surface stain treatment was evaluated in the following three stages.

A: No dirt adhered.

B: 〃 Somewhat acceptable.

C: 〃 Remarkably recognized.

The above test results are shown in Table 2.

As is clear from Table 2, Comparative Samples 101 to 102, which do not use the compound of the present invention, cause unevenness in processing and surface stain, which is a problem. On the other hand, Samples 103 to 105 using the compound of the present invention satisfy all of the coating property, the static mark test, the processing unevenness and the surface stain, which shows that the present invention is excellent.

Example 2 (Emulsion layer) A potato-like silver iodobromide emulsion containing 1.4 mol% of silver iodide and having an average grain size of 0.6 μm was prepared using ammonia.
This emulsion was chemically sensitized by adding 3 mg of chloroauric acid per 1 mol of silver and 10 mg of sodium thiosulfate per 1 mol of silver, and then 4-hydroxy-6-methyl-1,3,3a7-as an antifoggant. 70 mg of tetrazaindene per 1 mol of silver,
Olimer Latex (poly (ethyl acrylate / methacrylic acid = 97: 3) particles adsorbed with poly (degree of polymerization 10) oxyethylene dodecyl ether (3% by weight of particles)) (0.4 g / m ² ), poly Sodium acrylate, matting agent (Poly (methyl methacrylate / dodecyl fluoroheptyl acrylate = 80: 20) particles (particle size about 2.0μ) (0.02
The following compound BW-1 (3% by weight of particles) adsorbed in g / m ² ) and trimethylolpropane were added in advance.

(Preparation of coating solution for protective layer) Acid-treated gelatin 0.8 g / m ² Sodium polyacrylate 0.05 〃 Potassium polystyrene sulfonate 0.04 〃 Dextran (molecular weight about 20,000) 0.7 〃 Polyacrylamide (molecular weight about 80 thousand) 0.2 〃 Poly (methyl) Acrylate / methacrylic acid (7: 3) average particle size 4.5μ 0.02〃 poly (methyl acryle) (average particle size 3.0) 0.01〃 poly (degree of polymerization 10) oxyethylene cetyl ether 0.03
〃 Fluorine-containing compounds 1,2-bis (vinylsulfonylacetamide) ethane 0.1
The compounds of the present invention were added to the above compounds as shown in Table 3 to prepare a gelatin coating solution for protective layer (gelatin concentration 8%).

(Preparation of polymer layer) A coating liquid for polymer layer having the following contents was prepared.

Gelatin 0.5g / m ² Polymer A 0.0575g / m ² Poly (degree of polymerization 10) oxy ethylene cetyl ether 0.005g / m ² polymer (thickener) (Preparation of Photo Film) A polymer film, an emulsion layer and a protective layer were simultaneously coated on both sides of a polyethylene terephthalate support (thickness 180 μm) to prepare a photo film. The coated silver amount was 6 g / m ^{2 on} one side.

The following tests were performed on each sample thus obtained.

(Coatability) The same method as in Example 1 was followed.

(Static Mark) The static mark was evaluated in the same manner as in Example 1.

The development processing is carried out using an automatic processor FMP-4000 (development RD-III (35 ° C.)-Fixing (Fuji-F) -washing-drying, 90 seconds processing) commercially available from Fuji Photo Film Co., Ltd. It was

(Fixing solution contamination) Sample that produces Dmax1.2 by X-ray exposure (25 cm x 30 c
m) were continuously treated with FPM-4000 for 500 sheets. (At this time, the replenishment amount of the developing solution and the fixing solution was 50% of the specified standard amount).

The insoluble suspended matter of the fixing solution after the processing was evaluated according to the following four stages.

A: No floating material is observed.

B: Floating matter is slightly observed.

C: Equivalent 〃 D: 〃 Remarkably 〃 (Image unevenness) An image was formed on the sample uniformly exposed by X-ray so that the density after development was 0.8.

The compositions of the developing solution and the fixing solution are as follows.

<Developer> Potassium hydroxide 17g Sodium sulfite 60g Diethylenetriamine pentaacetic acid 2g Potassium carbonate 5g Boric acid 3g Hydroquinone 25g Diethylene glycol 12g 4-Hydroxymethyl-4-methyl 1.65g-1-Phenyl-3-pyrazolidone 5-methylbenzotriazole 0.6g Acetic acid 1.8g Potassium bromide 2g Adjust to 1 with water (adjust to pH 10.35).

<Fixer> Ammonium thiosulfate 140g Sodium sulfite 15g Ethylenediaminetetraacetic acid / 25mg Disodium dihydrate / Sodium hydroxide 6g Adjust to 1 with water (acetic acid pH 4.95). The developing process is as follows.

Processing temperature, time Development 35 ° C × 11.5 seconds Fixing 35 ° C × 12.5 seconds Washing 20 ° C × 7.5 seconds Drying 60 ° C Dry to Dry processing time 60 seconds The unevenness on the image of the obtained sample was evaluated by the following four grades.

A: No unevenness is observed on the image.

B: 〃 Somewhat acceptable.

C: There is considerable unevenness on the image.

D: 〃 Remarkably 〃 Table 3 shows the test results.

As shown in Table 3, sample 20 containing the compound of the present invention.
Samples Nos. 1 to 205 are excellent samples that satisfy all of the coating property, the static mark, the fixing liquid stain property, and the image unevenness. On the other hand, the control of Sample 206 is inferior to that of the present invention in all respects, and Samples 207 to 209 using Comparative Compounds a, b, and c are also markedly poor in terms of static marks, fixing solution contamination, and image unevenness.

From the above results, it can be easily said that the sample of the present invention is remarkably excellent in every respect.

Example 3 (Preparation of Emulsion Coating Solution) 30 g of gelatin, 5 g of potassium bromide and 0.05 g of potassium iodide were added to 1 part of water, and a silver nitrate aqueous solution (5 g as silver nitrate) and iodide were added with stirring in a container kept at 75 ° C. An aqueous potassium bromide solution containing 0.73 g of potassium was added by the double jet method over 1 minute. Further silver nitrate aqueous solution (145g as silver nitrate)
And potassium bromide aqueous solution were added by the double jet method.
At this time, the flow rate was accelerated so that the flow rate at the end of the addition was 8 times that at the start of the addition. Then, 0.37 g of an aqueous potassium iodide solution was added.

After the addition was completed, the soluble salts were removed at 35 ° C by the precipitation method, the temperature was raised to 40 ° C, and 60 g of gelatin was added to adjust the pH to 6.5. The temperature is raised again to 56 ° C and the sensitizing dye anhydro-
5,5'-di-chloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt 650 mg was added, and then chemical sensitization using gold and sulfur sensitization was performed. I did it.

The obtained emulsion has a hexagonal tabular shape and a projected area diameter of 0.85 μm.
The average thickness was 0.158 μm.

4-Hydroxy-6-methyl- was added to this emulsion as a stabilizer.
1,3,3a, 7-tetrazaindene and 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine,
Trimethylolpropane and dextran as dry antifoggants (added so that the molecular weight is about 40,000 and the coating amount is 0.4 g / m ² ). Polymer latex (poly (ethyl acrylate / styrene sulfonic acid = 96: 4) particles were used in Example 2
Pre-treated with compound BW-1 (3% by weight of particles) in -1, average particle size 0.1 μm (0.5 g / m ² ), matting agent (poly (methyl methacrylate / methacrylic acid = 95:
5) Particles previously treated with poly (polymerization degree 10) oxyethylene P-nonylphenoxy ether (3% by weight of particles), (particle diameter 2.5 μm) (0.02 g / m ² ), potassium polystyrene sulfonate Sodium polyacrylate was added to prepare a coating solution for emulsion layer.

(Preparation of Coating Solution for Protective Layer) The following gelatin solution was prepared as a coating solution for the surface protective layer.

Acid-treated gelatin 0.8 g / m ² Sodium polyacrylate 0.04 〃 Potassium polystyrene sulfonate 0.03 〃 Dextran (molecular weight 40,000) 0.8 〃 Polyacrylamide (molecular weight 70,000) 0.2 〃 Poly (methyl methacrylate / glycidyl acrylate = 90/10) ( Dispersion in gelatin with particle size 0.35 μm (gelatin concentration 6%) 0.025 g (as particles), poly (methyl methacrylate) (average particle size 1.5 μm) 0.01 g
/ m ² poly (degree of polymerization 10) oxyethylene cetyl ether 0.035
〃 Fluorine-containing compounds 1,2-bis (vinylsulfonyl lacetamide) ethane
0.2 〃 To this, the compound of the present invention or the comparative compound was added as shown in Table 4.

(Preparation of Support) The latexes of styrene / butadiene in colored polyethylene terephthalate support to blue, further gelatin 0.08 g / m ² as an upper layer, the polymer A (Example 2-2 according 0.058 g / m ² ) And dye (compound SS-1 0.017
g / m ² ) Dichlorohydroxytriazine (0.01 g / m ² ) was applied on both sides and dried to prepare a support.

(Preparation of Photographic Film) A coating solution for emulsion layer and a coating solution for protective layer were simultaneously coated on both sides of the support and dried to obtain a sample. The coated silver amount is one side 1.
It was set to 9 g / m ² .

With respect to the sample thus prepared, the coating property, the static mark, the fixing solution contamination and the image unevenness were examined in the same manner as in Example 3. However, the following developing processes were used.

<Developer> Potassium hydroxide 56.6g Sodium sulfite 200g Diethylenetriaminepentaacetic acid 6.7g Potassium carbonate 16.7g Boric acid 10g Hydroquinone 83.3g Diethylene glycol 40g 4-Hydroxymethyl-4-methyl-1-phenyl-3
-Pyrazolidone 11.0 g 5-methylbenzotriazole 2 g Potassium bromide 6 g Water is added to make 3 l.

(PH adjusted to 10.15) <Fixer> Ammonium thiosulfate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid / disodium dihydrate 0.10g Sodium hydroxide 24g Water to make 4l (adjust to pH 5.10 with acetic acid).

Processing time in an automatic processor is: development 35 ℃ 12 seconds, fixing 25 ℃ 9
Second, washing with water at 20 ° C. for 8 seconds, and Dry to Dry for a total of 45 seconds.

As is clear from Table 4, samples using the compound of the present invention
Nos. 301 to 305 have excellent coating properties, static marks, stains on the fixing solution, and image unevenness. In contrast, the control sample
309 and comparative samples 306 to 308 do not satisfy all of coating property, static mark, fixing solution contamination, and image unevenness.

From the above, it can be seen that the present invention is significantly superior to the conventional techniques.

It is clear that the present invention exerts an excellent effect especially when a rapid processing at a high speed which has not been heretofore achieved.

Example 4 (Preparation of coating solution for emulsion layer) An emulsion layer coating solution was prepared in the same manner as in Example 3 except that the following slab-like twinned grains were used in place of the hexagonal tabular emulsion of Example 3. Prepared.

28g of gelatin, 30g of potassium bromide and 4.5g of potassium iodide were added to 850cc of water, and ammoniacal silver nitrate (45g as silver nitrate) was added to the potassium bromide aqueous solution simultaneously for 10 minutes while stirring in a container kept at 38 ° C. They were added simultaneously by the double jet method. After the addition, the pH was adjusted to 5 with acetic acid, and then 105 g of silver nitrate was simultaneously added in the form of an aqueous solution simultaneously with the aqueous solution of potassium bromide over 40 minutes using the double jet method. After the addition is completed, by the sedimentation method
After removing the soluble salts at 35 ° C, the temperature was raised to 40 ° C and 75 g of gelatin was added to adjust the pH to 6.4. The obtained emulsion is thick plate-like grains, and the average diameter of a circle having the same area as the projected area (hereinafter referred to as the projected area diameter) is 0.63 μm.
m, the average thickness was 0.30 μm, and the silver iodide content was 3.07 mol%. This emulsion was chemically sensitized by combining gold and sulfur sensitization to obtain an emulsion.

(Preparation of Coating Solution for Emulsion Layer Protective Layer) It was prepared in exactly the same manner as in Example 3.

(Preparation of Batsuku layer coating solution) Gelatin 1.5 g / m ² Polymethyl methacrylate (particle size 0.7 [mu] m) N-oleoyl taurate Sozo um salt 0.005 〃 Indianapolis sauce Nru acid 0.05 〃 (Preparation of Batsuku protective layer coating solution) Prepared exactly as in Example 3.

(Preparation of Support) The support was prepared in exactly the same manner as in Example 3.

(Preparation of Photographic Film) A coating solution for backing layer and a coating solution for protective layer for backing layer were coated on one side of the above-mentioned support and the coating solution for emulsion layer and coating solution for emulsion layer were coated on the other side to prepare a sample No. 5 I made it like the table.

The amount of silver in the emulsion layer was adjusted to 3.2 g / m ² .

The obtained sample was tested in exactly the same manner as in Example 3. The results are shown in Table 5.

As is clear from Table 5, samples using the compound of the present invention
Nos. 401 to 405 have excellent coating properties, static marks, stains on the fixing solution, and image unevenness, and it can be seen that the present invention is significantly superior to the comparison.

The sample obtained in the present invention was also excellent in practical images.

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion layer or another hydrophilic colloid layer has the following general formula [I]: A silver halide photographic light-sensitive material containing a compound represented by: In the general formula (I) _{A-X-YB n SO 3} M type, A is an alkyl group, an alkenyl group of 8 to 25 carbon atoms,
Represents an aryl group, X is -O-, And R is an alkyl group or Y-B. Y is at least Unit is included, a is 0 to 50, and b is 1
~ 50. B represents a divalent linking group (provided that The group is excluded. ). n represents 0 or 1. M represents a cation.