JP2904889B2 - Silver halide photographic material and processing method thereof - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material). The present invention relates to a photosensitive material in which contamination by light is reduced and a method for processing the photosensitive material.

BACKGROUND OF THE INVENTION In recent years, there has been a demand in the art for rapid processing of photosensitive materials.

Photosensitive materials are usually processed continuously by automatic developing machines provided at each development site.However, as part of improving services for users, development processing is performed within It is required to be returned, and recently, even within a few hours of reception, it has been required, and the need for quick processing has been increasing. Further, the reduction of the processing time leads to the improvement of the production efficiency and the reduction of the cost, so that the development of the rapid processing is urgently required.

In order to achieve rapid processing, approaches have been made from two aspects: a photosensitive material and a processing solution. For color development processing,
Attempts to increase the temperature, increase the pH, increase the concentration of the color developing agent, and the like have been attempted, and it is also known to add additives such as a development accelerator. As the development accelerator, British Patent 811,
No. 185, 1-phenyl-4-pyrazolidone, U.S. Pat.No. 2,417,514, N-methyl-p-aminophenol, and JP-A-50-15554, N, N, N ', N'-tetramethyl-p -Phenylenediamine and the like. However, these methods do not achieve sufficient rapidity, and often involve performance deterioration such as an increase in fog.

On the other hand, it is known that the shape, size and composition of silver halide grains of a silver halide emulsion used for a light-sensitive material greatly affect the development speed, etc. It has been found that a very high development rate is exhibited when silver halide having a high ratio is used.

Accordingly, a technique using a photosensitive material containing silver halide grains composed of a high concentration of silver chloride (for example, Japanese Patent Application Laid-Open No. 58-95)
Nos. 345, 58-95736, and 60-19140) give particularly excellent speed-up performance.

However, when such a high silver chloride-containing photosensitive material is continuously subjected to running processing, the problem has been clarified that the adhesiveness of the surface of the photosensitive material is increased, which causes various inconveniences in handling and storing finished prints. This adhesion of the photosensitive material surface refers to a phenomenon in which, particularly when the photosensitive material is placed in a high-temperature and high-humidity atmosphere, the photosensitive material surface sticks and adheres to various substances that come into contact with the photosensitive material. During the manufacture or storage of photosensitive materials, they are often wound in a roll or stacked in a sheet.At this time, the adhesion between the emulsion side surface and the back surface of the support, which is likely to occur, or during photography, Adhesion to components of the device during exposure and development processing, and adhesion during storage of finished prints in albums, etc., pose problems.

Techniques for improving this adhesion problem include, for example, as described in JP-A-51-6017 and JP-A-53-116143, known as matting agents in the art, such as colloidal silica, A technique is known in which fine particles of an inorganic substance such as silicon dioxide, titanium dioxide, magnesium oxide, and calcium carbonate, or fine particles of an organic substance such as polymethyl methacrylate and cellulose acetate propionate are contained in a surface layer. However, when such a matting agent is contained, there is a problem that the surface gloss of the photosensitive material is deteriorated.

Further, the high silver chloride-containing light-sensitive material excellent in rapid processing suitability has a drawback that a physical development reaction is caused by a sulfite usually contained in a color developing solution, resulting in insufficient dye concentration. For this reason, high silver chloride-containing light-sensitive materials are destined to be used in a concentration region in which sulfite is extremely low.

However, when a photosensitive material containing high silver chloride is processed with a color developing solution having a low sulfite concentration, sufficient rapidity can be obtained, but when the bleach-fixing process is subsequently performed, the concentration of the sulfurous acid, a preservative in the color developing solution, is increased. Is low, the color developing agent is oxidized, and so-called bleaching fog is likely to occur.
Sulfite is also very effective in preventing coloring of the color developing solution, so if the sulfite concentration is low, the color developing solution tends to be colored, and oxides of the color developing agent adhere to the photosensitive material during processing. And there is a problem that contamination occurs.

As an improvement technique for this, Japanese Patent Application Laid-Open No. 63-229457 discloses that an acid-treated gelatin having an isoelectric point of 6.0 to 9.5 is used in an amount of 25% by weight or more of the total coated gelatin amount of a light-sensitive material.
However, in this case, a sufficient effect cannot be obtained on the above-mentioned increase in the adhesiveness of the surface, and acid-treated gelatin having an isoelectric point of 6.0 to 9.5 is likely to adversely affect photographic performance, resulting in desensitization and unsensitized. There is a problem that the storage stability of the processed sample is deteriorated.

On the other hand, in a method of continuously running a photosensitive material, it is generally practiced to perform a running process while replenishing a replenisher of each processing solution in order to prevent a change in characteristics of a finished print due to a change in the concentration of the processing solution. Is being done. However, in this case, a large amount of overflow liquid is generated with the replenishment of the replenisher, which is a serious problem in terms of pollution and cost. Therefore, reduction of the replenishment amount (low replenishment) of the color developing solution has been strongly desired in recent years. However, if the high-speed silver halide-containing photosensitive material excellent in rapid processing suitability is continuously processed with a low-replenished color developing solution,
The above-mentioned problem that the adhesion of the finished print surface is remarkably increased becomes apparent.

[Problems to be Solved by the Invention] As described above, in silver halide photographic materials excellent in rapid processing suitability, techniques for reducing surface adhesion and contamination due to processing are not satisfactory.
Improvement is desired.

Accordingly, the present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a silver halide photographic light-sensitive material capable of rapid processing.

A second object of the present invention is to provide a silver halide photographic material having reduced surface adhesion.

A third object of the present invention is to provide a silver halide photographic light-sensitive material in which contamination due to processing is reduced.

A fourth object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material capable of reducing the replenishment amount of a color developing solution.

[Means for Solving the Problems] The object of the present invention is to provide a silver halide photographic light-sensitive material having a photographic component layer comprising at least one light-sensitive silver halide emulsion layer on a support. At least one of the silver halide emulsion layers contains 90 mol% or more of silver halide grains composed of silver chloride, and at least one of the photographic constituent layers contains at least 43% by weight of an α component having a molecular weight of about 100,000. This is achieved by a silver halide photographic material characterized by containing gelatin.

The replenishment amount of the light-sensitive material of the present invention is 1 m ²
The effect of the present invention is more effectively exhibited when processing is carried out with a color developing solution of 20 to 150 ml per unit.

[Specific Configuration of the Invention] The present invention will be described in more detail below.

The silver halide grains according to the present invention have a silver chloride content of 90 mol% or more, a silver bromide content of preferably 10 mol% or less, and a silver iodide content of 0.5 mol%. The following is preferred.

According to the present invention, even if the silver chloride content is higher, sufficient gradation reproducibility is obtained, and silver chlorobromide having a silver bromide content of 0.1 to 2 mol% can be more preferably used.

The composition of the silver halide grains according to the present invention may be uniform from the inside to the outside of the grains, or the inside and outside compositions of the grains may be different. When the inside and outside compositions of the particles are different, the composition may be changed continuously or may be discontinuous.

Examples of such silver halide grains are disclosed in
No. 95736 and No. 58-108533.

Various methods known in the art can be used as the apparatus and method for preparing a silver halide emulsion.

The silver halide grains used in the photographic emulsion according to the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time, or may be grown after seed particles have been made.

The form in which the soluble silver salt is reacted with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method and a combination thereof, but a method obtained by a consensus mixing method is preferable. Further, as one form of the double jet method, a pAg-controlled double jet method described in JP-A-54-48521 can be used.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Patent No. 2,921,164 A device for continuously changing the concentration of an aqueous solution of a water-soluble silver salt and a water-soluble halide salt as described in JP-A-56-501776, taking out the reaction mother liquor from the reactor described in Publication No. 56-501776, and performing ultrafiltration. An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by a method may be used.

If necessary, a silver halide solvent such as thioether or imidazole may be used. A nitrogen-containing heterocyclic compound such as a mercaptotetrazole compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The grain size of the silver halide grains of the present invention is not particularly limited, but is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.1, in consideration of other photographic properties such as rapid processing property and sensitivity.
The range is 2 μm. In addition, the said particle diameter can be measured by various methods generally used in the said technical field. Representative methods include Loveland's "Particle Size Analysis" (ASTM Symposium on Right Microscopy, 1955, pp. 94-122) or "Theory of Photographic Processing" (Mies and James, 3rd ed.
Edition, Chapter 2 of Macmillan Publishing Company (1966)).

The particle size can be measured using the projected area of the particle or the approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse. Monodisperse silver halide grains having a coefficient of variation of preferably 0.22 or less, more preferably 0.15 or less, in the particle size distribution of the silver halide grains are preferred. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Here, ri represents the particle size of each particle, and ni represents its number. The particle size referred to here is the diameter of a spherical silver halide particle, or the diameter of a cubic or non-spherical particle when the projected image is converted to a circular image of the same area. .

The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. US Patent
Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, etc., and the Journal of Photographic Science (J. Photgr. Sci), 2
According to a method described in a document such as 1,39 (1973), particles having an octahedral, tetrahedral, or dodecahedral shape can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

The silver halide grains used in the photographic emulsion according to the present invention are formed in a step of forming and / or growing.
Metal ions are added using 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 a complex salt thereof, and /
Alternatively, the sensitizing nucleus can be provided on the inside of the grain and / or on the surface of the grain by placing it in an appropriate reducing atmosphere.

In the emulsion containing the silver halide grains according to the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or the emulsion may be kept contained. Good. The removal of the salts can be carried out according to the method described in Research Disclosure No. 17643.

The emulsion of the present invention is chemically sensitized by a conventional method. That is,
Sulfur sensitization using compounds containing sulfur that can react with silver ions, active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, noble metal sensitization using gold or other noble metal compounds Etc. can be used alone or in combination.

Known sensitizing dyes can be used in the silver halide photographic light-sensitive material of the present invention. These dyes include a cyanine dye having a thiazole nucleus, a selenazole nucleus, an oxazole nucleus, and an imidazole nucleus as two basic nuclei in which a benzene ring or a naphthalene ring is condensed; Nucleus, 2-thioselenazolidine-2,4-dione nucleus, merocyanine dye having a barbituric acid nucleus as an acidic nucleus, trinuclear complex merocyanine dye having three mother nuclei, and cyanine dye is highly sensitive And can be advantageously used.

These sensitizing dyes may be used in combination of a plurality of dyes depending on the required spectral sensitivity distribution and the like.

 Hereinafter, specific examples of the sensitizing dye preferably used are shown.

Preferred compounds for the green photosensitive sensitizing dye include the following.

Preferred compounds as the red-sensitive sensitizing dye include the following.

Specific compounds of the infrared sensitizing dye used in the present invention are listed below, but the present invention is not limited only to these compounds.

The infrared sensitizing dye used in the present invention is used in an amount of 5 × 10 ^{-7 to} 5 × 10 ^-3 mol, preferably 1 × 10 ^-6 to 1 per mol of silver halide.
It is used in an amount of × 10 ^-3 mol, particularly preferably 2 × 10 ^{-6 to} 5 × 10 ^-4 mol.

The red-sensitive sensitizing dye and the infrared sensitizing dye can be used in combination with the following compounds as a supersensitizer.

Hereinafter, the gelatin used in the present invention will be described.

Gelatin usually used in the photographic industry includes, in the production process from collagen, alkali-treated gelatin accompanied by treatment with lime and acid-treated gelatin accompanied by treatment with hydrochloric acid and the like. Manufactured as a raw material.

For details on the production method and properties of these gelatins, see
For example, `` The Macromolecular Chemistry '' by Arthur Veis
of Gelatin ", Academic Press, 187-217 (1964),
THJames: The Theory of the Photographic Process 4
th.ed. 1977, (Macmillan) p. 55, Handbook of Scientific Photography (top) 72
Pp. 75 (Maruzen), Fundamentals of Photographic Engineering-Silver Halide Photography, 119-124
Page (Corona).

For the molecular weight of gelatin, see D. Lorry and M. Vedrin
es, Proceedings of the 4ht IAG Conference, Fribourg,
As described in Sept., 1983, p.35, Takashi Ohno, Hiroyuki Kobayashi, Shinya Mizusawa, Journal of the Photographic Society of Japan, 47,237 (1984), etc., the alpha component (molecular weight of about 10
10,000) and its dimer, trimer, β component and γ component, high molecular weight component as multimer, and low molecular weight component in which these components are irregularly cut. It is. The measurement of the gelatin molecular weight distribution is based on the above literature,
JP-A-60-80838, JP-A-62-87952, JP-A-62-265645, JP-A-60-80838
As described in 279329, 64-46742 and the like, gel permeation chromatography (hereinafter referred to as “GPC method”)
Is written). The ratio of the α component of the gelatin used in the present invention can be determined by the GPC method under the following conditions.

(GPC method) a) Column: Asahipak, GS-620 (manufactured by Asahi Kasei Kogyo Co., Ltd.) Two in series connection Temperature 50 ° C b) Eluent: Equivalent mixing of 0.1 M KH ₂ PO ₄ and 0.1 M Na ₂ HPO ₄ Solution pH 6.8 Flow rate 1.0 ml / min c) Sample: 0.2% eluent of gelatin Solution injection volume 100 μl d) Detection: UV absorption spectrophotometer (UV wavelength 230 nm) Retention time 230 nm
(FIG. 1) showing the change in the absorption of gelatin, the peak of the exclusion limit first appeared, and then the γ component, β component and α component of gelatin.
The peaks due to the components appear one after another, and as the retention time becomes longer, the shape becomes like a tail.

The proportion of the α component in the present invention can be determined by calculating the proportion of the area of the peak of the α component in the entire chart to the entire area. More specifically, a line b perpendicular to the horizontal axis is drawn from the minimum point on the left (in the direction of smaller retention time) of the peak a of the α component appearing at the 23rd minute of the retention time. Next, a line c perpendicular to the horizontal axis is drawn at a position of +1.5 minutes from the peak a by the retention time. The ratio of the area surrounded by the measurement curves, b, c and the baseline to the total area is calculated.

The proportion of the α component determined by the above method of the gelatin used in the present invention is 43% by weight or more, more preferably 45% by weight.
% Weight or more.

In the present invention, when the desired gelatin is obtained by blending gelatins having different values of the α component, even if any of the gelatin components is 43% by weight or less, the ratio of the α component to the total colloid after blending is not limited. What is necessary is just 43% by weight or more.

The proportion of the high molecular weight component of the gelatin used in the present invention is preferably 3% or less. Here, the proportion of the high molecular weight component in the present invention can be determined by calculating the proportion of the area of the exclusion limit peak to the entire area. Specifically, draw a vertical line on the horizontal axis from the minimum point next to the peak that appears at the retention time of about 15 minutes, and calculate the ratio of the area of the part (high molecular weight component) on the left side of the vertical line to the total area Required by

The gelatin of the present invention may be lime-processed gelatin, acid-processed gelatin, or may be gelatin made from any of bovine bone, cow hide, pork skin and the like, and preferably from bovine bone. It is manufactured lime-processed gelatin.

Jelly strength of gelatin of the present invention (by puggy method)
Is preferably 250 g or more.

The calcium content (according to the Paggy method) of the gelatin of the present invention is preferably 1000 ppm or less, particularly preferably 500 ppm or less. In order to reduce the calcium content in gelatin, generally, treatment with an ion exchange resin column is preferably used.

Further, the gelatin of the present invention can be subjected to an oxidation treatment with hydrogen peroxide or the like for the purpose of reducing photographic activity.

In obtaining the gelatin of the present invention, α having a molecular weight of about 100,000
Means for increasing the components include, for example, the following means.

 Adjust the conditions such as the period and temperature of the lime treatment of the raw material.

The temperature and time for extracting the gelatin from the pretreated raw material into the aqueous phase are adjusted, and the extraction is performed at a relatively low temperature of 50 to 60 ° C. Generally, the extraction is performed in the order of a first extraction, a second extraction, and a third extraction. The first extract is preferable, and the extraction is preferably performed in a short extraction time.

When the extracted gelatin solution is concentrated, gelled, and dried to obtain gelatin, it is performed at a temperature as low as possible (40 ° C. or less) to prevent decomposition by heat. Preferably, a vacuum concentration method or a concentration method by ultrafiltration is used.

 A molecular weight fractionation method using an ultrafiltration membrane is used.

A molecular weight fractionation method by a coacervation method using an organic solvent such as alcohols is used.

The gelatin of the present invention can be obtained by using these means alone or in combination.

The silver halide photographic light-sensitive material of the present invention may be composed of a single photographic constituent layer or a plurality of photographic constituent layers. When it comprises a plurality of photographic constituent layers, it is particularly preferred that the gelatin of the present invention is contained in the surface protective layer provided farthest from the support, in order to exert the effects of the present invention.

The gelatin contained in the silver halide photographic light-sensitive material of the present invention is hardened by a hardener. The hardening system that can be used is not particularly limited, and known hardening agents in the photographic industry: for example, aldehyde hardening agents, active vinyl hardening agents, active halogen hardening agents, epoxy hardening agents, Examples thereof include an ethyleneimine hardener, a metal sulfonate hardener, a carbodiimide hardener, an isoxazole hardener, and a polymer hardener.

The hardener preferably used in the present invention is a vinyl sulfone-based hardener shown below and / or a general formula [H-
A chlorotriazine-based hardener represented by the formula [I] or [H-II].

Vinyl sulfone hardeners preferably used in the present invention include, for example, aromatic compounds described in German Patent 1,100,942 and heterocyclic compounds described in JP-B-44-29622 and JP-B-47-25373. Alkyl compounds linked by base paper, sulfonamides and ester compounds as described in JP-B-47-8736, and 1,3,5-tris (β-β) as described in JP-A-49-24435. (Vinylsulfonyl) propionyl] -hexahydro-s-triazine or an alkyl compound as described in JP-A-51-44164.

Representative compounds are shown below, but are not limited thereto.

Vinyl sulfone hardeners preferably used in the present invention are, in addition to the above-mentioned exemplified compounds, compounds having at least three vinyl sulfone groups in the molecular structure, for example, exemplified compounds [H-5] to [H-22] And a compound having a group that reacts with a vinyl sulfone group and a compound having a water-soluble group, such as diethanolamine, thioglycolic acid, sarcosine sodium salt, and taurine sodium salt.

In the formula, R ¹ and R ² are each a chlorine base paper, a hydroxyl group,
Alkyl group, alkoxy group, alkylthio group, -OM group (where M is a monovalent metal atom), -NR ³ R ⁴ group (where R ³ and R ⁴ are a hydrogen atom, an alkyl group, respectively) or an aryl group) or a -NHCOR ⁵ (wherein, R ⁵ represents a hydrogen atom, an alkyl group or an aryl group). However, R ¹ and R ² are not chlorine atoms at the same time.

Wherein R ⁶ and R ⁷ are each a chlorine atom, a hydroxyl group,
An alkyl group, an alkoxy group or an -OM 'group (where M'
Is a monovalent metal atom). Q 'and Q "each represent a substituent representing -o-, -s- or -NH-;
Represents an alkylene group or an arylene group. p and q each represent 0 or 1.

The chlorotriazine-based hardener represented by the general formula [HI] (cyanuric chloride-based hardener) is described in U.S. Pat. No. 3,645,743, JP-A-47-6151, JP-A-47-33380,
No. 51-9607, JP-A-48-19220, JP-A-51-78788,
52-60612, 52-128130, 52-130326, 56-1
No. 043, which can be used.

The bischlorotriazine hardener represented by the general formula [H-II] (biscyanuryl hardener) is described in Canadian Patent 895,808, JP-B-58-33542, and JP-A-57-40244. It is described and can be used.

Next, typical specific examples of the compound represented by the general formula [HI] or [H-II] will be described, but the present invention is not limited thereto.

Compounds represented by the general formula [HI]: Compound represented by the general formula [H-II]: In the present invention, the vinyl sulfone hardener and the hardeners represented by the above formulas [HI] and [H-II] are used for the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention and other hydrophilic compounds. It is used to increase the film strength of the hydrophilic colloid layer, and diffuses into all the layers to be coated, so that at least one layer or a plurality of layers are selected from the emulsion layer or the auxiliary layer according to the present invention and added. Good. The addition is dissolved in water or alcohol (eg, methyl alcohol, ethyl alcohol, etc.),
Preferably, 1 to 100 mg is added per 1 g of gelatin. The addition method may be either a batch method or an inline method. The timing of addition is not particularly limited, but is preferably added immediately before coating.

The swelling ratio (the thickness of the hydrophilic colloid layer in the processing solution / the thickness of the hydrophilic colloid layer in a dry state) of the silver halide photographic light-sensitive material of the present invention is preferably 1.5 to 4.0, more preferably 2.0 to 4.0. 3.0.

As the color developing agent used in the color developing solution used in the present invention, a p-phenylenediamine compound having a water-soluble group is preferable.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material than the p-phenylenediamine-based compound not having a water-soluble group such as N, N-diethyl-p-phenylenediamine, and has no effect on the skin. It has the advantage that the skin is less susceptible to fogging.

Examples of the water-soluble group include those having at least one on an amino group or a benzene nucleus of a p-phenylenediamine-based compound, and specific water-soluble groups include-(CH ₂ ) nCH
_{2 OH, - (CH 2)} mNHSO 2 (CH 2) nCH 3, - (CH 2) mO (CH 2) nCH 2, - (CH 2 CH 2 O) nCmH 2m + 1 (m and n are each 0 or more Represents an integer of.) —COOH group, —SO ₃ H group and the like are preferred.

As the color developing agent preferably used in the present invention,
Exemplary color developing agents described in JP-A-62-249151 (A
-1) to (1-16).

Among them, preferred for use in the present invention is exemplified No.
(A-1), (A-2), (A-3), (A-4),
Compounds represented by (A-6), (A-7) and (A-15), and particularly preferably (A-1: N-ethyl-N-β-).
Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate).

The color developing agent is usually used in the form of a salt such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The color developing agent used in the present invention is usually preferably used in the range of 0.1 g to 20 g per edible developer, more preferably in the range of 0.5 g to 10 g per edible developer.

In a conventional color developer, a sulfite is usually used as one of the preservatives in an amount of about 8 × 10 ^-3 to 4 × 10 ^-2 mol per color developer, but the conventional system is applied to the present invention. As a result, a decrease in color density, which is considered to be caused by physical dissolution development of silver chloride, occurs.

Accordingly, the color developing solution used in the present invention has a sulfite concentration of preferably 4 × 10 ⁻³ mol or less, more preferably 2 × 10 ^{−3 to} 0 mol per color developing solution.

Examples of the sulfite used in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

When the compound represented by the following general formula (I) is used in the color developer used in the present invention instead of hydroxylamine conventionally used as a preservative, the storage stability of the color developer is improved. It is particularly preferably used in the present invention because it is improved and silver development by hydroxylamine does not occur when a photosensitive material containing high silver chloride is used.

In the general formula (I), R ₁ and R ₂ each have 1 to 1 carbon atoms.
3 represents an alkyl group, wherein R ₁ and R ₂ may be the same or different and include, for example, a methyl group, an ethyl group, a propyl group, an i-
And a propyl group.

R ₁ and R ₂ are preferably both ethyl groups.

Specific examples of the compound represented by the general formula [I] include (I-1) to (I-6) described in JP-A-62-249151.
And the like.

These compounds are usually used in the form of hydrochloride, sulfate, p-toluenesulfonate, acid salt, phosphate, acetate and the like.

The concentration of these compounds in the color developer is similar to that of hydroxylamine, which is usually used as a preservative,
For example, 0.1 to 50 g / l is preferably used, more preferably 1 to 30 g / l, and particularly preferably 3 to 15 g / l.

The color developing solution used in the present invention includes JP-A-62-2491.
It preferably contains an amine compound such as (D-1) to (D-17) described in No. 51.

In the color developer of the present invention, in addition to the above preservative components, hydroxamic acids, hydrazines, hydrazides, α-hydroxyketones, α-aminoketones, various sugars, polyethyleneimines, aromatic polyhydroxy compounds etc,
Preservatives known in the photographic art can be used.

In the color developer of the present invention, in addition to the above color developer components, for example, an alkali agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium tertiary phosphate, potassium carbonate, potassium hydrogen carbonate; methanol, ethanol,
Organic solvents such as butanol, ethylene glycol, and diethylene glycol; development regulators such as citrazic acid and polyethylene glycol; chelating agents such as dihydroxybenzenes, dihydroxynaphthalenes, aminopolyphosphonic acids, oxycarboxylic acids, phosphonocarboxylic acids, and polyphosphoric acids A fluorescent whitening agent such as a 4,4'-diamino-2,2'-disulfostilbene compound; metol, phenidone, N, N'-
Diethyl-p-aminophenol hydrochloride, N, N, N ', N'
If necessary, various photographic additives known in the photographic field, such as an auxiliary developer such as -tetramethyl-p-phenylenediamine hydrochloride, can be contained.

Generally, a color developer often contains benzyl alcohol for the purpose of accelerating development and accelerating color formation. However, benzyl alcohol has pollution problems,
Further, it is not preferable in that it has poor solubility and poor solution preparation, and further promotes contamination of the developer. The content of benzyl alcohol in the color developing solution of the present invention is preferably 2 ml or less, and most preferably 0, per developing solution.

The color developing solution of the present invention preferably contains no or very small amount of water-soluble bromide. When the photosensitive material contains an excessive amount of water-soluble bromide, the developing speed of the photosensitive material decreases. The bromide ion concentration in the color developing solution is generally 0.1 g or less, preferably 0.05 g or less per color developing solution in terms of potassium bromide.

It is preferable to use a water-soluble chloride as a development regulator in the color developing solution.

The amount of the water-soluble chloride used is preferably 0.5 g to 5 g per color developing solution in terms of potassium chloride, more preferably 0.5 g to 5 g.
Used in the range of 1 g to 3 g.

In the color developing solution, an organic development inhibitor described in JP-A-58-95345 can be further used within a range not to impair the present invention. Preferably, adenine and guanines are used in the color developing solution in the range of 0 to 0.02 g / l.

In the present invention, when the photosensitive material is subjected to continuous running processing, the replenishment amount of the color developing solution is from 20 to 1 per m ² of the photosensitive material.
It is preferably 150 ml, more preferably 20 to 100 ml
a / m ^2.

The pH of the developing solution of the present invention is preferably 9.5 or more, more preferably 13 or less. It is conventionally known that the development is accelerated by increasing the pH of the developer,
In the present invention, sufficient rapid developability can be obtained even when the pH is 11 or less.

The temperature of the color developing solution is preferably from 15 to 45 ° C, more preferably from 20 to 40 ° C.

Conventionally, the color development time is about 3 minutes and 30 seconds, but in the present invention for the purpose of rapidity, it can be made within 2 minutes, and preferably in the range of 20 seconds to 1 minute.

In the present invention, a bleaching process and a fixing process are performed after color development. The bleaching process may be performed simultaneously with the fixing process. Many compounds are used as the bleaching agent. Among them, polyvalent metal compounds such as iron (III), cobalt (III), and copper (II), particularly, complex salts of these polyvalent metal cations and organic acids, for example, ethylenediaminetetraacetic acid Metal complex salts such as aminopolycarboxylic acids such as nitrilotriacetic acid, N-hydroxyethylethylenediamine diacetate, malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid or ferricyanates, dichromates, etc. Alone or in an appropriate combination.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea, thioether and the like.

After the fixing process, a washing process is usually performed. For water washing, water with reduced calcium and magnesium using an ion exchange resin or the like may be used. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination. The stabilizing solution used for the stabilizing treatment may contain a pH adjuster, a chelating agent, a deterrent and the like. These specific conditions can be referred to JP-A-58-134636 and the like.

In the silver halide photographic material according to the present invention,
Any of yellow, magenta, and cyan couplers currently known can be preferably used. An example of such a coupler will be described.

Hereinafter, specific examples of the yellow coupler preferably used in the present invention will be described, but the present invention is not limited thereto.

Hereinafter, specific examples of the magenta coupler preferably used in the present invention will be described, but the present invention is not limited thereto.

Hereinafter, specific examples of the cyan coupler preferably used in the invention will be described, but the invention is not limited thereto.

The preferred addition amount of the above yellow coupler is 2 × 10 ⁻³ to 2 mol, more preferably 1 × 10 ⁻² to 1 mol, per 1 mol of silver halide.

The addition amount of the above magenta coupler is preferably 1 × 10 ⁻³ to 2 mol, more preferably 1 × 10 ⁻² to 1 mol, per 1 mol of silver halide.

The amount of the cyan coupler to be added is preferably 1 × 10 ⁻³ to 2 mol, more preferably 1 × 10 ⁻² to 1 mol, per 1 mol of silver halide.

When an oil-in-water emulsion dispersion method is used to add a hydrophobic compound such as a coupler to a silver halide emulsion, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C or higher, if necessary. Dissolve with a low boiling point and / or water-soluble organic solvent in combination and disperse it in a hydrophilic binder such as an aqueous gelatin solution using a surfactant with a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic device, etc. After emulsifying and dispersing using a means, it may be added to the desired photographic constituent layer (hydrophilic colloid layer).

After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be added.

Examples of high boiling organic solvents used for such purposes include dibutyl phthalate and di- (2-ethylhexyl).
Phthalates such as phthalate, dinonyl phthalate, dicyclohexyl phthalate, tricresyl phosphate, tri- (2-ethylhexyl) phosphate,
Phosphoric acid esters such as di-phenyl-cresyl phosphate and trihexyl phosphate; organic acid amides such as diethyl lauryl amide and dibutyl lauryl amide; phenols such as dinonyl phenol and p-dodecyl phenol; and carbonization such as decalin and dodecyl benzene. Hydrogens, 1,
Esters such as 4-bis (2-ethylhexylcarbonyloxymethyl) cyclohexane and dinonyl adipate are preferably used. Among them, phthalic acid, phosphoric acid,
Other organic acid esters are more preferably used. These high-boiling organic solvents may be used alone or in combination of two or more.

Examples of the water-insoluble and organic solvent-soluble polymer used for dispersing the coupler and the like include (1) a vinyl polymer and a copolymer (2) a polycondensate of a polyhydric alcohol and a polysalt acid, and (3) a ring opening weight. Polyester obtained by a method (4) Others Polycarbonate resin, polyurethane resin, polyamide resin and the like.

The number average molecular weight of these polymers is not particularly limited,
Preferably not more than 200,000, more preferably 5,000 to 10
It is ten thousand. Ratio of polymer to coupler (weight ratio)
Is preferably 1:20 to 20: 1, more preferably 1:10 to 10: 1.
It is.

Specific examples of the polymer preferably used are shown below.
The copolymer showed the weight ratio of the monomers.

(PO-1) Poly (Nt-butylacrylamide) (PO-2) Nt-butylacrylamide-methyl methacrylate copolymer (60:40) (PO-3) Polybutyl methacrylate (PO-4) methyl Methacrylate-styrene copolymer (90:10) (PO-5) Nt-butylacrylamide-2-methoxyethyl acrylate copolymer (55:45) (PO-6) ω-methoxy polyethylene glycol acrylate (addition mole) Number n = 9) -Nt-butylacrylamide copolymer (25:75) (PO-7) 1,4-butanediol-adipate polyester (PO-8) polypropiolactam In order to increase the durability of the image dye, various compounds can be used. Among them, the compounds represented by the following general formulas [a] and [b] described in JP-A-62-166339 have no drawbacks such as lowering the coloring property of the coupler and impairing the effects of the present invention. Can be preferably used.

In the formula, R ₄₁ and R ₄₂ each represent an alkyl group. R ₄₃ represents an alkyl group, a —NR′R ″ group, a —SR ′ group (R ′ represents a monovalent organic group) or a —COOR ″ group (R ″ represents a hydrogen atom or 1
Represents a valent organic group. ). m represents an integer of 0 to 3.

In the formula, R ₄₄ is a hydrogen atom, a hydroxyl group, an oxy radical group (—O group), a —SOR ′ group, a —SO ₂ R ′ group (R ′ is 1
A monovalent organic group), an alkyl group, an alkenyl group or an alkynyl group, or a -COR "group (R" represents a hydrogen atom or a monovalent organic group).

R ₄₅ , R ₄₆ , R ₄₅ ′, R ₄₆ ′ and R ₄₉ each represent an alkyl group. R ₄₇ and R ₄₈ are each a hydrogen atom or a —OCOR ₅₀ group (R
₅₀ represents a monovalent organic group. Or R ₄₇ and R ₄₈ may together form a heterocyclic group. n is 0
Represents an integer of 4.

The alkyl group represented by R ₄₁ and R ₄₂ in the general formula [a] is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably a branched alkyl group having 3 to 8 carbon atoms at the α-position. . R ₄₁ and R ₄₂ are particularly preferably a t-butyl group or a t-pentyl group.

The alkyl group represented by R ₄₃ is a straight-chain or branched one, such as methyl, ethyl, propyl, butyl, pentyl, octyl, nonyl, dodecyl,
Octadecyl group and the like. This alkyl group includes those having a substituent. The amino group represented by R ₄₃ is an alkylamino group, an arylamino group, a cycloalkylamino group,
Includes heterocyclic amino groups and the like.

The monovalent organic groups represented by R ′ and R ″ include, for example, an alkyl group, an aryl group, a cycloalkyl group, and a heterocyclic group. These organic groups include those having a substituent.

Formula [b] is preferably an alkyl group represented by R ₄₄ of from 1 to 12 carbon atoms, alkenyl or preferably an alkynyl group, a 2 to 4 carbon atoms,
The monovalent organic groups represented by R ′ and R ″ are, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and the like.

The alkyl group represented by R ₄₅ , R ₄₆ , R ₄₅ ′, R ₄₆ ′ and R ₄₉ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group. It is.

In R ₄₇ and R ₄₈ , examples of the monovalent organic group represented by R ₅₀ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylamino group, an arylamino group.

The following are typical examples of the above compounds.

Exemplary compound of general formula [a] Exemplary compound of general formula [b] The silver halide photographic material of the present invention includes a color fogging inhibitor, a hardener, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger, a development accelerator, a development retarder, a fluorescent brightener, a matting agent, A lubricant, an antistatic agent, a surfactant and the like can be optionally used.

The photographic constituent layers of the silver halide photographic light-sensitive material of the present invention may be baryta paper or paper laminated with an α-olefin polymer or the like, a paper support from which the α-olefin layer can be easily separated from the paper support, or a synthetic paper. Flexible reflective support, reflective support or metal, ceramics containing or coated with a film white pigment made of semi-synthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. Can be applied to a rigid body or the like. Or 120-1
A thin reflective support of 60 μm can also be used.

As the white pigment, an inorganic and / or organic white pigment can be used, and preferably an inorganic white pigment, for example, a sulfate of an alkaline earth metal such as barium sulfate, or a carbonate of an alkaline earth metal such as calcium carbonate. Salt, finely divided silica, synthetic silicate silica, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc,
Clay and the like. The white pigment is preferably barium sulfate or titanium oxide.

The silver halide light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, directly or undercoating (adhesion, antistatic property, It may be applied via one or more subbing layers to improve degree stability, rub resistance, hardness, antihalation, frictional properties and / or other properties.

When coating a photographic light-sensitive material using the silver halide emulsion according to the present invention, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

[Examples] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

Example 1 Nine kinds of silver halide emulsions shown in Table 1 were prepared by a neutral method and a double jet method.

After the completion of chemical sensitization, each of the silver halide emulsions was added with 2 × 10 ⁻⁴ mol of the following STAB-1 as an emulsion stabilizer per mol of silver halide.

Next, the following layers 1 to 7 were successively applied (simultaneously applied) on a paper support having both surfaces coated with polyethylene, whereby a silver halide color photographic light-sensitive material 101 was produced. (The amount of addition is shown per 1 dm ² of the light-sensitive material.) Layer 1: gelatin a (12 mg), 2.9 mg (in terms of silver, the same applies hereinafter) blue-sensitive silver halide emulsion (EmB-1) and 7.5
mg of yellow coupler (YY-1), 3 mg of light stabilizer STB-
1 and 0.15 mg of 2,5-dioctylhydroquinone (HQ-
A layer containing 3 mg of dinonyl phthalate (DNP) dissolved in 1).

Layer 2: 2 mg in which gelatin (9 mg) and 0.4 mg of HQ-1 are dissolved
Layer containing DOP (dioctyl phthalate).

Layer 3: Gelatin a (14 mg), 2 mg of green light-sensitive silver halide emulsion (EmG-1) and 6 mg of magenta coupler (MM-
1), 3 mg of DOP in which 2.5 mg of light stabilizer STB-2 and 0.1 mg of HQ-1 were dissolved and 0.06 mg of the following filter dye AIM-1
A layer containing

Layer 4: gelatin a (12 mg) and the following 6 mg of UV absorber U
Layer containing 3 mg of DNP dissolved in V-1 and 0.5 mg of HQ-1.

Layer 5: gelatin a (14 mg), 2 mg of red-sensitive silver halide emulsion (EmR-1), and 2 mg of cyan coupler CC-
Layer containing 1.3 mg of cyan coupler CC-8 and 3 mg of DOP dissolved in 0.1 mg of HQ-1.

Layer 6: 2 mg of gelatin a (11 mg) and 2 mg of UV-1 dissolved
Containing DOP and 0.05 mg of the following filter dye AIC-1.

Layer 7: Layer containing gelatin a (10 mg).

In addition, as a hardening agent, Exemplified Compound (I-1) was added to Layers 2, 4 and 7 so as to be 0.01 g per 1 g of gelatin in all layers.

Next, the gelatin and silver halide emulsion of Sample 101 are shown in Table 1.
Samples 102 to 110 were produced by changing the configuration as shown in FIG.

However, gelatins a to d in Table 2 are as follows.

Gelatin a: Lime-processed gelatin containing bovine bone as raw material 35% Gelatin b: Lime-processed gelatin obtained from bovine bone as raw material Combination of means for increasing α component described in the text Contains α component Ratio 43% gelatin c: content of gelatin α component obtained by treating gelatin b using an ultrafiltration membrane 48% gelatin d: content of α component of intermediate fraction obtained by fractionating gelatin b using ethanol coacervation 59 % Gelatins a and b are subjected to an ion exchange treatment, and the calcium contents of gelatins a to d are all 500 ppm or less.

In addition, after coating the photographic constituent layers, each sample was cooled once to set a gelatin layer, and then dried at 40 ° C. to prepare a sample.

Further, these samples were kept at 35 ° C. and a relative humidity of 60% for 5 days to form a hardened film.

The sample thus prepared was exposed according to a conventional method, and then processed according to the following processing steps.

Processing temperature Temperature Color development 35.0 ± 0.3 ° C 45 seconds Bleaching and fixing 35.0 ± 0.5 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60-80 ° C 60 seconds Color developing solution Pure water 800 ml Triethanolamine 10 g N, N-diethyl Hydroxylamine 5 g potassium bromide 0.02 g potassium chloride 2 g potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g ethylenediaminetetraacetic acid 1.0 g catechol-3,5-disulfonic acid disodium salt 1.0 g N-ethyl- N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 4.5 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium carbonate 27 g Add water to make the total amount 1 and adjust the pH to 10.10.

Bleaching-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) 27.5ml Add water to 1 and adjust the pH to 1 with potassium carbonate or glacial acetic acid. 6.
Adjust to 2.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% aqueous solution) 3.0 g Ammonium sulfite 3.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Add water to make the total amount 1 and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

 The following evaluation was performed about the obtained processed sample.

<Sensitometry> Blue light (B), green light (G), red light (R), respectively
(S) and minimum density of unexposed area (Dmin)
I asked.

<Evaluation of gloss> The gloss of the surface of the treated sample was measured by Nippon Denshoku Industries Co., Ltd.
The measurement was performed with a VG-ID type gloss meter at an incident angle of 60 ° and a light receiving angle of 60 °.

<Evaluation of Adhesiveness> The sample was cut into a square of 4 cm, and the humidity was adjusted at 23 ° C. and a relative humidity of 80% for 10 hours. Lay the surfaces of the conditioned samples on top of each other 50
g / cm ² with weight again at 23 ° C, relative humidity 8
Measure the adhesive area when humidifying for 10 hours under 0% condition,
The area of the bonded portion was determined in percent.

 The results are shown in Table-3.

Among the samples 101 and 102 using silver halide grains outside the present invention, the sample 102 using the gelatin of the present invention in which the α component content is 43% by weight or more has improved adhesiveness and glossiness. As can be seen, both Samples 101 and 102 have low sensitivity and poor rapid processing. On the other hand, Samples 103 to 110 using the silver halide grains of the present invention are all high in sensitivity and excellent in rapid processing suitability, but Samples 103 and 105 not using the gelatin of the present invention were all adhered. In addition, the color density is inferior, and the minimum density is high. In contrast, all of the samples 104 and 106 to 109 of the present invention using the silver halide grains of the present invention and the gelatin of the present invention have improved adhesiveness, and have a lower minimum density and improved color contamination. It can be seen that the gloss is high. The sample 110 using the matting agent is excellent in adhesiveness, but is not preferable because a large deterioration in glossiness and an increase in color contamination are observed. Among the samples of the present invention, the content of the α component is
Samples 107 and 108 using 45% by weight or more of gelatin are found to be particularly excellent in adhesiveness and glossiness. In addition, comparing the sample 106 using only the surface protective layer of the gelatin of the present invention with the sample 109 using the whole layer,
Although the effect of the present invention is larger in the sample 109 used for all layers, the effect is also large in the sample 106 used only for the surface protective layer, and by using the gelatin of the present invention for the surface protective layer, the present invention is more efficient. It can be seen that the effects of the invention can be obtained.

Example 2 On a support in which polyethylene was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the other side, each layer having the following structure was applied on the side of the polyethylene layer containing titanium oxide. Thus, a multilayer silver halide color photographic light-sensitive material sample 201 was prepared. The coating solution was prepared as described below.

First layer coating solution Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67
g, additive (HQ-1) 0.67g and high boiling point organic solvent (DNP)
60 ml of ethyl acetate was added to 6.67 g to dissolve, and this solution was
Using an ultrasonic homogenizer, the mixture was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of a surfactant (SU-1) to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

In addition, (HH-1) was added to the second and fourth layers as a hardener.
(HH-2) was added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

DOP dioctyl phthalate DNP dinonyl phthalate DIDP diisodecyl phthalate PVP polyvinylpyrrolidone (Preparation of Blue-Sensitive Silver Halide Emulsion) The following (Solution A) and (Solution B) were simultaneously added to 1000 ml of a 2% aqueous gelatin solution kept at 40 ° C. over 30 minutes while controlling pAg = 6.5 and pH = 3.0. The following (Solution C) and (Solution D) were simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water 200 ml (Solution B) Add 10 g of silver nitrate water and 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Add water and 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.85 μm. Thus, a monodisperse cubic emulsion EMP-1 having a coefficient of variation (σ /) = 0.07 and a silver chloride content of 99.5 mol% was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to give a blue-sensitive silver halide emulsion (Em-
B) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS− 21.times.10.sup.- ⁴ mol / mol AgX (Preparation method of green-sensitive silver halide emulsion) Addition time of (solution A) and (solution B) and (C solution) and (D
EMP-2), except that the addition time of the solution was changed, to obtain a monodispersed cubic emulsion EMP-2 having an average particle diameter of 0.43 μm, a coefficient of variation (σ /) = 0.08, and a silver chloride content of 99.5 mol%. Was.

EMP-2 was chemically ripened at 55 ° C. for 120 minutes using the following compound to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (red-sensitive halogenated Preparation method of silver emulsion) Addition time of (Solution A) and (Solution B) and (Solution C) and (D
EMP-3), except that the addition time of the liquid was changed, to obtain a monodisperse cubic emulsion EMP-3 having an average particle size of 0.50 μm, a coefficient of variation (σ /) = 0.08, and a silver chloride content of 99.5 mol%. Was.

EMP-3 was chemically ripened at 60 ° C. for 90 minutes using the following compounds to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX Next, the gelatin of Sample 201 was changed as shown in Table-5,
Samples 201 to 208 were produced.

Gelatins ad in Table-5 are the same as those used in Example 1.

After exposing the sample prepared in this manner according to a conventional method,
In accordance with the following processing steps, the color developing solution tank capacity of 3
Continuous processing was performed until a double amount of the color developing replenisher was replenished. Processing temperature / time Color development 35.0 ± 0.3 ° C 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60-80 ° C 60 seconds The composition of each processing solution is shown below.

The replenishment amount of the color developing solution is 1 m ^{2 of} silver halide photographic material.
A is 160 ml, B is 110 ml, and C is 80 ml.

Bleach-fix solution (the tank solution and the replenisher are the same) Ethylenediaminetetraacetate ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (tank solution and replenisher solution are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Fluorescent brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Add water to make the total volume 1 and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide. .

 The following evaluation was performed on the obtained treated sample.

<Evaluation of Color Contamination> Dmin was determined for the processed sample at the start of the continuous processing and the processed sample at the end of the continuous processing in the same manner as in Example 1, and the difference ΔDmin between the two was determined.

<Evaluation of Adhesive Property> The treated samples at the start of the continuous processing and at the end of the continuous processing were evaluated for the adhesive property in the same manner as in Example 1.

 The results are shown in Table-6.

As is clear from Table-6, all of the samples 201 using gelatin other than the present invention have a large ΔDmin and an increase in color contamination due to continuous processing, and also have a large surface adhesiveness. On the other hand, all of the samples 202 to 208 of the present invention using the gelatin of the present invention have a small ΔDmin, reduce the increase in color contamination due to continuous processing, and have low surface adhesiveness. Further, it can be seen that the sample of the present invention can increase the color contamination and suppress the surface adhesiveness to a low level even when a processing step with a small replenishment amount is performed. Furthermore, in the processing step with a small amount of replenishment, among the samples of the present invention, samples 203, 204, 207 and 208 using gelatin having an α component content of 45% by weight or more showed increased color contamination due to continuous processing, It can be seen that the effect of suppressing the increase in is excellent.

Example 3 Samples 301 to 3 were prepared in the same manner as in Example 2 except that the gelatin in the seventh layer of Sample 201 of Example 2 was changed as shown in Table-7.
05 was created. The same evaluation as in Example 2 was performed using this sample. The results are shown in Table-7.

Gelatins e to i are lime-processed gelatins using the following bovine bones as raw materials.
Was created by combining.

As is clear from Table 7, all of the samples of the present invention using the gelatin of the present invention have a small increase in color contamination due to the continuous treatment and a low surface adhesion. It can be seen that among the present invention, gelatin having a high molecular weight component content of 3% by weight or less is preferable in view of the effects of the present invention.

Example 4 HH-3, HH-4, HH-5, HH-6 were used in place of the hardeners HH-1 and HH-2 used in the samples prepared in Example 2.
Alternatively, a sample using HH-7 was prepared, and the same items as in Example 2 were evaluated. As a result, the effect of the present invention was obtained.

HH-3 = the above exemplified compound H-23 HH-4 = H H-24 HH-5 = 〃 II-2 Example 5 Each layer having the following constitution contains titanium oxide on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide and a blue dye (ultra blue) on the other side. Apply on the polyethylene layer side,
A multilayer silver halide color photographic material sample 501 was prepared. The coating solution was prepared as described below.

First layer coating solution 19.1 g of yellow coupler (YX-1), 4.4 g of dye image stabilizer (STX-1) and 1.4 g of polymer compound (PX-1)
g of high-boiling point organic solvent (SX-1) 8.2 g and ethyl acetate 28.
0 ml was added to dissolve, and this solution was 185 ml of 10% aqueous gelatin solution containing 8 ml of 10% sodium dodecylbenzenesulfonate.
The resulting mixture was emulsified and dispersed in ml to prepare a yellow coupler dispersion. This dispersion was mixed and dissolved with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating liquids for the second to seventh layers were also prepared in the same manner as the coating liquid for the first layer. Exemplified compound (I-1) as a hardening agent
Was used. The following water-soluble dyes were added to the emulsion layer to prevent irradiation.

Blue-sensitive silver chlorobromide emulsion (EmX-B) Cube Average grain size 0.86 μm Coefficient of variation of grain size distribution 0.08 Locally containing 0.2 mol% of silver bromide on the grain surface After adding the following blue-sensitive sensitizing dye, sulfur Give sensitization.

Green-sensitive silver chlorobromide emulsion (EmX-G) Cube Average particle size 0.55 μm and 0.38 μm mixed at 1: 3 (A
(g mol ratio) Coefficient of variation of grain size distribution 0.10 and 0.08 Locally contained 0.8 mol% of silver bromide on the grain surface After adding the following green-sensitive sensitizing dye, sulfur sensitization is performed.

Red-sensitive silver chlorobromide emulsion (EmX-R) Cube Average particle size 0.59 μm and 0.45 μm mixed at 1: 4 (A
(g mole ratio) Coefficient of variation of grain size distribution 0.08 and 0.11 0.6 mol% of silver bromide is contained locally at a part of the grain surface. After adding the following red-sensitive sensitizing dye and supersensitizer, sulfur is added. Give sensitization.

In addition, blue-sensitive emulsion, green-sensitive emulsion, red-sensitive emulsion, STBX
-1 was added in an amount of 8.0 × 10 ^-5 mol, 7.5 × 10 ^-5 mol and 2.6 × 10 ^-4 mol per mol of silver halide, respectively.

Next, gelatin a of sample 501 was replaced with gelatin b or c.
Were prepared, and the same items as in Example 2 were evaluated using the following processing steps. As a result, the effects of the present invention were obtained.

(The three-tank countercurrent system was set to stable →.) The composition of each processing solution was as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Glacial acetic acid 9g Add water 1000ml pH (25 ℃) 5.40 Stabilizer (Tank solution and replenisher are the same) Formalin (37%) 0.1 g Formalin-sulfite adduct 0.7 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4 -Isothiazolin-3-one 0.01 g Copper sulfate 0.005 g Ammonia water (28%) 2.0 ml Add water 1000 ml pH (25 ° C) 4.0 [Effect of the invention] The present invention has excellent suitability for rapid processing and excellent surface adhesion. Further, a silver halide photographic light-sensitive material in which color contamination due to processing was reduced could be provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a chart showing the change in absorption at 230 nm depending on the retention time.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/047 G03C 1/035 G03C 7/44

Claims (2)

(57) [Claims] 1. A silver halide photographic material having a photographic component layer comprising at least one photosensitive silver halide emulsion layer on a support, wherein at least one of said photosensitive silver halide emulsion layers is 90 mol. % Or more of silver halide grains comprising at least one silver halide
A silver halide photographic material, wherein the layer contains gelatin containing at least 43% by weight of an α component having a molecular weight of about 100,000. 2. A method for processing a silver halide photographic material according to claim 1 with a color developing solution containing a color developing agent, wherein the replenishment amount of the color developing solution is per 1 m ^{2 of the} silver halide photographic material. A method for processing a silver halide photographic light-sensitive material, wherein the amount is 20 to 150 ml.