JPH03253839A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic film having high sensitivity, satisfactory fixability and dryability by incorporating a water soluble polymer and gelatin contg. a specified amt. of alpha-component having a specified mol. wt. separated by gel chromatography into a hydrophilic colloidal layer. CONSTITUTION:A water soluble polymer and gelatin contg. >=40 wt.% alpha-component having about 100,000 mol. wt. separated by gel chromatography are incorporated into a hydrophilic colloidal layer. The synthetic water soluble polymer may be a polymer having nonionic groups, anionic groups or both nonionic and anionic groups in the molecular structure. The gelatin may be alkali treated gelatin obtd. by treatment with lime, tec., in a stage for producing gelatin from collagen or acid treated gelatin obtd. by treatment with hydrochloric acid, etc. A photographic film having satisfactory fixability, superior dryability, high sensitivity and high covering power is obtd.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photographic material provided with a light-sensitive silver halide emulsion layer, and more specifically to a photographic material having a high covering power and good fixing properties and drying properties. This invention relates to a sensitive silver halide photographic material.

[Background of the invention]

Silver halide photographic material (hereinafter referred to as photographic film)
The essential constituent layer is a hydrophilic colloid layer containing dispersed silver halide grains, that is, a photosensitive emulsion layer, and other photographic properties,
It consists of photographic constituent layers such as a hydrophilic colloid layer (auxiliary layer) that assists or complements the physical properties, and photographic properties such as sensitivity, granularity, and sharpness are essential and essential properties. As processing becomes automatic and faster, processing performance such as developability and fixing performance is questioned, as well as quality assurance of reproducibility and stability, as well as cooling gelation rate, jelly strength, drying rate, etc. Productivity is considered to be an issue.

It is thought that the overall gelling structure of the hydrophilic polymer, including the micelle structure of gelatin forming the hydrophilic colloid layer, has a decisive influence on the processability, gelation, drying rate, etc. It will be done. That is, it is thought that the permeability of water and chemicals, the resistance to deformation of silver halide grains during development, etc. strongly depend on the gelled structure.

Furthermore, in black-and-white photographic film that utilizes the optical density developed by developed silver, the coat linkage of developed silver is
ring power (hereinafter referred to as cp), that is, the optical density per unit of developed silver is an important characteristic that affects the density of photographic images.The more highly dispersed the developed silver is, the finer metallic silver filaments, the higher High (gives a high concentration. Therefore, during development, the gelled structural state of the colloid layer and L'?T must have room for the developed silver to become highly dispersed silver. However, if it is too fine, Since it is a six-colored colloidal silver 2, there must be a preferable range for its gelled structural state.

Further 1. :EP speeds up processing 1. Therefore, it is desirable that the response of the optimum gelling structure state during processing be fast.

For the purpose of increasing EP, two drugs for CP and 1. Many technologies have been proposed in the past, such as U.S. Pat. Nos. 2,271.158 and 3,51 using polyacrylamide.
Representative examples include US Pat. No. 4,063,838 and US Pat. No. 3,272,631, which use dextran.

1, or 1. Therefore, many of these conventional CP-directed technologies have some kind of drawback1,5. When used, after development IA and treatment, the film 13 has devitrification 1, 2,
Fixing properties during development processing are reduced, and drying properties are also deteriorated.

[Purpose of the invention]

An object of the present invention is to provide a photographic film with high cp, high sensitivity, good fixing properties, and good drying properties.

[Structure of the invention]

The object of the present invention is to provide the gel 1. of the photographic constituent layer of the photographic film 1. As a result, in a silver halide photographic light-sensitive material in which a photographic constituent layer consisting of at least one hydrophilic colloid layer is provided on both sides or one side of the support surface, in the hydrophilic colloid layer n. The σ component of approximately 100,000 molecules is separated using gel chromatography.
The object of the present invention could be distantly achieved by a silver halide photographic light-sensitive material characterized by containing Qwt% or more of gelatin and a water-soluble polymer.

The present invention will be explained in detail below.

Gelatin commonly used in the photographic industry includes alkali-processed gelatin, which involves treatment with lime or other substances during the production process from collagen, and acid-processed gelatin, which involves treatment with hydrochloric acid. It is manufactured using raw material such as pork skin and L7.

For details on the manufacturing method, properties, etc. of these gelatins, see, for example, Arguchi 1u ``The Maero+n'' by Veis.
oleeutoar Che+m1stry of Ge
1atinJ, AcadeIIic Presyt
.

pp. 187-217 (1964 pm), T. H. James.
AuthorThe Theory of the Photog
rapic ProcessJ 4th, cd,
1977゜(Mae+n1llan) 5S page, "Science copy
0nasha) etc.

Regarding the molecular weight of gelatin, D, 1. orry an
dM, Vedrines, Proceedings
of the 4tb IAG Conference
ce, Fribourg, 5ept, 198:
Lp, 35, Rikuyo Ohno, Hiroyuki Kobayashi, Shinya Mizusawa, Journal of the Photographic Society of Japan, 47.237 (1984) etc.
(about 100,000 molecular weight), its dimer and trimer β component, γ component, and multimer polymer g1. Boat fishing consists of component 1 components, and furthermore, low-molecular landscape components in which these components are irregularly cut.

When gelatin has a large amount of high molecular weight components, it gels quickly,
Although the jelly strength is high, the gel structure is too dense to meet the purpose of the present invention.

The measurement of gelatin molecular leaf distribution is described in the above-mentioned literature and Japanese Patent Application Laid-open No. 1983
-80838, 62-87952, 62-26
No. 5645, No. 62-27932Q, No. 64-467
42, etc., gel chromatography-shicon chromatography, rGPC method) i. 'Therefore, do 1. Invention 1: The proportion of the α component in the gelatin used is determined by the GPC method in Section 1 below.

(GPC method) a) Carano: Asabipak, Gs-620
(manufactured by Asahi Kakogyo Co., Ltd.) 2 columns connected in series Column temperature 50°C b) Solution n: O. 1M-KH, PO, and Q. lvN
Equal volume mixed solution with aJPOa pH 6.8 Flow rate 1.0
mQ/minC) Sample: Gelatin 062% eluent solution injection volume +00/III! d) Detection: Ultraviolet absorption spectrophotometry (UV wavelength 230 nm) Retention Time
Chart showing changes in absorption of 230■ due to (Fig. 1)
The peak of the exclusion limit appears first, and then the γ of gelatin
Peaks due to the component, β component, and α component appear sequentially, and as the retention time becomes longer, the shape becomes more tail-like.

The ratio of the α component specified in the present invention can be determined by calculating the ratio of the area of the peak of the α component to the total area in the above chart. Specifically, a line perpendicular to the horizontal axis is drawn from the minimum point to the left of the peak a of the α component that appears at about 23 minutes of retention time (in the direction where the retention time is smaller). Next, a line C perpendicular to the horizontal axis is drawn at a position of +1.5 minutes in retention time from peak a. The ratio of the area of the area surrounded by the measurement curves b, c, and the baseline to the total area is calculated.

α determined by the above method of gelatin used in the present invention
The proportion of the components is 4Qwt% or more, more preferably 4Qwt% or more.
It is 5 wt% or more.

Note that the ratio of the α component in the present invention is determined by blending gelatins with different values of the α component to obtain the desired gelatin.
Even if the content of any gelatin component is 4Qwt% or less, it suffices as long as its proportion to the entire colloid after blending is 40wt% or more.

Furthermore, the proportion of the high molecular weight component in the gelatin used in the present invention is preferably 3% or less. It can be determined by calculating the ratio using the area method.

Specifically, a perpendicular line is drawn on the horizontal axis from the minimum point next to the peak that appears at around 15 minutes of retention time, and the ratio of the area of the area to the left of the perpendicular line (high molecular weight component) to the total area is calculated. required by.

The gelatin of the present invention may be lime-treated gelatin or acid-treated gelatin, or may be gelatin made from cow bone, cow skin, pig skin, etc., but preferably from cow bone. The product is lime-processed gelatin.

The jelly strength (by baggy method) of the gelatin of the present invention is:
Preferably it is 250g or more.

Calcium content of gelatin of the present invention (by baggy method)
is preferably lo00 ppm or less, particularly preferably 500 ppm or less. To reduce the calcium content in gelatin, treatment with an ion exchange resin column is generally preferred.

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

In obtaining the gelatin of the present invention, α with a molecular weight of about 10,000
Examples of means for increasing the components include the following means.

■Adjust the period, temperature, and other conditions for lime treatment of raw materials.

(2) Adjust the temperature and time when extracting gelatin from the pretreated raw material into the aqueous phase, and extract at a relatively low temperature of 50 to 60°C. Generally, extraction is performed sequentially as a first extraction, a second extraction, and a third extraction, but the first extraction is preferred, and it is further preferred that the extraction be performed in a short extraction time.

■ When concentrating, gelatinizing, and drying the extracted gelatin solution to obtain gelatin, do so at a low temperature (below 40°C) to prevent decomposition due to heat. Preferably, a vacuum concentration method or a concentration method using ultrafiltration is used.

■ Use molecular weight fractionation using an ultrafiltration membrane.

■ Use a molecular weight fractionation method based on the coacervation method using organic solvents such as alcohols.

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

The water-soluble polymer according to the present invention does not necessarily have to have a high solubility in water, but it must have at least a solubility in water.

For example, 0.05g for 100g of water at 20℃
As mentioned above, preferably 1 g or more of O is dissolved. The higher the solubility of the water-soluble polymer used in the developer or fixer, the better.
It is preferable to dissolve 0.05 g or more, more preferably 0.5 g or more, and especially 1 g or more.

Examples of synthetic water-soluble polymers that can be used in the present invention include those having a nonionic group, an anionic group, and both a nonionic group and an anionic group in their molecular structure. Here, examples of the nonionic group include an ether group, an ethylene oxide group, and a hydroxy group. Examples of the anionic group include a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and the like.

The synthetic water-soluble polymer may be a homopolymer or a copolymer. The copolymer may be a copolymer with a partially hydrophobic monomer, as long as the polymer itself is water-soluble.

Preferred water-soluble polymers include those containing repeating units of the following general formula CI), particularly those containing to-100 mol % of the units in one polymer molecule.

Furthermore, these synthetic water-soluble polymers have been disclosed in a West German patent application (O
LS) No. 2,312,708, U.S. Patent No. 3,620,
No. 751, No. 3,879,205, Special Publication No. 43-75
It can be obtained by the synthesis method described in No. 61, etc., or a method analogous thereto.

General formula [I] In the formula, R1 and R2 may be the same or different and each represents a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group,
(butyl group, etc.), a halogen atom, or CH2C00M'.

L is -CONH-1-NHCO-1-COO-1-OC
O-1-CO-1SO, -5-NH5O, -1-SO,
Represents NH- or -O-.

J is an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms (e.g., methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc.)
Furthermore, these have substituents, etc.), arylene groups (
For example, phenylene group, etc., which further has a substituent, etc.), aralkylene 1 2 H represents an integer of 0 to 4. ) represents.

Further, Q represents a hydrogen atom or R3, where M l and M2 represent a hydrogen atom or a cationic group, and R1 represents an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group,
R3, R4, R6, R8, R7 and Ra are hydrogen atoms,
Alkyl groups having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hequinyl group, decyl group, hexadecyl group, etc., and those having substituents therein)
, alkenyl groups (e.g., vinyl groups, aryl groups, etc., or those having substituents thereon), phenyl groups (e.g., phenyl groups, methoxyphenyl groups, chlorophenyl groups, etc., or those having substituents thereon), aralkyl groups (e.g. benzyl group, etc. or those with substituents)
, X represents an anion, and p and q each represent 0 or l9゜Y is a hydrogen atom or +L+→J・
Represents h-Q.

The repeating unit represented by the general formula (I) may contain two or more types of monomer units in order to exhibit a composite function as a polymer.

The polymer in the present invention is a compound represented by the following general formula (II) containing 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more of the monomer represented by the general formula [■] as a polymer constituent unit. There may be.

3 14 General formula CI+) RI -(-cuzc-1-He0)+aa-8■ In the formula, X represents a mole percentage, and X is preferably 70 to 100.

In the formula, A represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer.

Examples of ethylenically unsaturated monomers in the preferred polymers of the invention are ethylene, propylene, butene, isobutyne, styrene, chloromethylstyrene, bitroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N,N , N-trimethyl-
N-vinylbenzylammonium chloride, N,N-
Dimethyl-N-benzyl-N-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluenepyridine, 2-vinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, l-vinyl-2-methylimidazole ,
Monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), ethylenically unsaturated mono- or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate) , potassium acrylate, sodium methacrylate)
, maleic anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. butyl acrylate, hexyl acrylate, hydroxyethyl acrylate, cyanoethyl acrylate, N,N-diethylaminoethyl acrylate, methyl methacrylate,
Butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N,N-triethyl-N-methacryloyloxyethylammonium-
p-) Luenesulfonate, NIN-diethyl-N-methyl-N-methacryloyloxyethylammonium-
P-toluene 15 16-sulfonate, dimethyl itaconate, maleic acid monobenzyl ester), and the like.

Next, specific examples of synthetic water-soluble polymers having the repeating unit of general formula (1) will be illustrated, but the present invention is of course not limited thereto.

Note that the numerical value enclosed in parentheses is the average molecular weight.

-1 -5 H3 -6- 7- -3 -9 -4 ■ 0 C) 12COOH 17- 18 I-11 ■ 2 (CH, -CH),. .

C0NHC3Hy(iso) (17,000) -13 -14 CH.

-15 9- ■ 1 (However, n: n2-50 mol% = 50 mol%, Mn-
approximately 10,000) ■ 2 (However, n: n2 = 75 mol% = 25 mol%, Mn =
Approximately 20,000) ■ 4 1 ■ 6 -17 ■ -18 ■ 9 ■ 0 CH.

20- ■ 5 ■ 6 ■ 7 ■ 8 22 (8,000) (11,500) ■ -29 When using the above synthetic water-soluble polymer, preferably its molecular weight is 1,000 to 100,000, more preferably 2,000 to 50,000 is used.

Among the above, examples 1-2 are particularly preferred polymers used in the present invention. Examples include l-6, 1-15, and the like.

The emulsion used in the film of the present invention may be any silver halide, such as silver iodobromide, silver iodochloride, silver iodochlorobromide, etc.; Silver oxide is preferred.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be a normal crystal such as a tetrahedron, a polyhedral crystal such as a sphere, a crystal formed from twins, or a mixed or composite type thereof.

The grain size of these silver halide grains may range from fine grains of 0.1 gm or less to large grains of up to 20 μm.

The emulsion used in the silver halide photographic material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978) - pp. 22-23.
ionPreparation and types
) and the same (RD) No. 18716 (1979 no. 11
It can be prepared by the method described on page 648.

Examples of the emulsion for the film of the present invention include T and H.

James, “The theory of the
photography pr.

G, F
, “Photographic Emulsion Chemistry” by Dauf Fin
graphic emulsion chemist
y”, Focalpress (1966), P.
, Glafkides, “Physics and Chemistry of Photography J” Ch.
imie at physique photogra
"Manufacturing and coating of photographic emulsions" by V. L. Zelikman et al.
otographic ea+ulsjon” Foc
It is prepared by the method described in, for example, published by Al Press (1964 noon).

That is, solution conditions such as neutral method, acidic method, ammonia method, mixing conditions such as forward mixing method, back mixing method, double jet method, Chondrald double jet method, conversion method, core/shell method, etc. Particle preparation conditions and combination methods thereof can be used.

A preferred embodiment of the present invention is a monodispersed emulsion in which silver iodide is localized inside the grains.

A monodisperse emulsion as used herein means that when the average particle diameter is measured by a conventional method, at least 95% of the particles in terms of number or weight are within ±40% of the average particle diameter, preferably within ±30%. It is a certain silver halide grain.

The grain size distribution of silver halide may be either a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

The crystal structure of silver halide may have different silver halide compositions inside and outside.

The emulsion as a preferred embodiment of the present invention is preferably a core/shell type monodisperse emulsion having a structure consisting of a high iodine core portion and a low iodine shell layer.

The silver iodide content of the high iodide portion of the present invention is 20 to 40 mol%, particularly preferably 20 to 30 mol%.

Methods for producing such monodispersed emulsions are known, for example, J. Ph.
ot, Sic, pp. 12.242-251 (1963)
, JP-A-48-36890, JP-A-52-16364,
No. 55-142329, No. 58-49938, British Patent No. 1,413,748, U.S. Patent No. 3,574.628
No. 3,655.394, etc.

As the above-mentioned monodisperse emulsion, an emulsion in which grains are grown by using seed crystals and supplying silver ions and halide ions using the seed crystals as growth nuclei is particularly preferred.

Note that methods for obtaining core/shell emulsions include, for example, British Patent No. 1,027,146 and US Patent No. 3,505.0.
No. 68, No. 4,444,877, JP-A-60-143
It is described in detail in issue 31.

The silver halide emulsion used in the present invention may be tabular grains having an aspect ratio of 5 or more.

Such tabular grains can improve spectral sensitization efficiency and improve image graininess and sharpness. These tabular grains are described in British Patent 2.112.15
No. 7, U.S. Pat. No. 4,439,520, U.S. Pat. No. 4,433.
No. 048, No. 414.310, No. 4,434,2
It can be prepared by the method described in No. 26, etc.

The emulsion mentioned above may be a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. good.

In these emulsions, cadmium salts, lead salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be used in the stage of physical ripening or grain preparation.

The emulsion was washed with noodle water to remove soluble salts, 7
Water washing methods such as zero curation sedimentation method or ultrafiltration method may be used. Preferred water washing methods include, for example, the method using an aromatic hydrocarbon aldehyde resin containing a sulfo group as described in Japanese Patent Publication No. 35-16086, or the method described in Japanese Patent Publication No. 16086
Agglomerated polymer agent example G 3 described in No. 3-158644,
A particularly preferred desalting method includes a method using G 8 or the like.

Various photographic additives can be used in the emulsion according to the present invention in the steps before and after physical ripening or chemical ripening.

Known additives include, for example, Research Disclosure No. 17643 (December 1978) and Research Disclosure No.
-18716 (November 1979).

The types of compounds shown in these two research disclosures and their descriptions are listed on the vestibule.

Additives Chemical sensitizers Sensitizing dye development accelerators Antifoggants Stabilizers Color stain inhibitors Image stabilizers Ultraviolet absorbers Filter dyes RD-17643 Page Classification 23 I[1 23IV 29 XI 24 Vl 25 ■ 25 ■ 25-26 ■〃 Rd-18716 Page Classification 648-Top right 648Right-649Left 648-Top right 649-Bottom right 650Left-Right 649Right-650Left 27 8 Brightener 24 V Hardening agent 26 X 651 Right coating aid 26-27 XI 65
0 right surfactant 26-27 II
650 right plasticizer 27 n
〃Slip agent 〃 Static prevention agent 27 ■ //
Matting agent 28 1VI 6
50 right binder 26 ff
651 Right Examples of the support that can be used for the film of the present invention include those described in the above-mentioned RD-17643, page 28, and RD-18716, page 647, left column.

Suitable supports include plastic films, and the surfaces of these supports may generally be provided with an undercoat layer or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve adhesion of the coating layer. The emulsion according to the present invention can then be coated on one or both sides of the support thus treated.

Although the present invention is applicable to all films, it is particularly suitable for high-speed black-and-white and color films.

When the present invention is applied to medical X-ray radiography, for example, a fluorescent intensifying screen whose main component is a phosphor that generates near-ultraviolet light or visible light upon exposure to penetrating radiation is used.

The penetrating radiation herein refers to high-energy electromagnetic waves, such as X-rays and gamma rays.

Further, the fluorescent intensifying screen includes, for example, an intensifying screen whose fluorescent component is mainly calcium tungstate, or a fluorescent intensifying screen whose main component is a rare earth compound activated with terbium.

〔Example〕

Next, the present invention will be explained by examples.

Example 1 (Preparation of seed crystals) The following solutions were prepared.

A liquid water
23ff potassium bromide
4.1g9- 30- Gelatin a 0.2kg B liquid water
5,2a potassium bromide
130g potassium iodide 3.6g
Gelatin A 110g0.2
N sulfuric acid 77ccC liquid water
6a potassium bromide 1
．． 90kg potassium iodide 54g
4g gelatin a l 50g D liquid water
5.44 Silver nitrate 19
0gE liquid water
6.4Q silver nitrate 2.
Solution A was placed in an 82 kg reaction vessel and kept at 60°C, and the other solutions were added at 59°C. At this time, liquids D and D were added over a period of 30 minutes using a controlled double jet method, and then liquids E and E were added over a period of 105 minutes using a controlled double jet method. Stirring at 800 rpm
I went with m. The flow rate is increased in proportion to the total surface area of the silver halide grains as the grains grow, so that new growth nuclei are not generated when the additive solution flows in, and so-called Ostwald ripening does not occur, and the grain size increases. It was added at a flow rate that did not spread the distribution. When adding silver ion solution and halide ion solution, pAg was 8.3±0. using potassium bromide solution.
The pH was adjusted to 2.0±0.1 using sulfuric acid. The obtained emulsion had a silver iodide content of 2 mol %, a grain size of 0.30 μm 1σ/y-0,11, and 5% of (111) planes, and the rest had slightly rounded corners consisting of (100) planes. The particles were cubic-shaped, tetradecahedral monodisperse particles.

After growing the seed crystals, adjust the pH to 6.0 using sodium carbonate solution.
After adjusting the temperature to 0 ± 0.3, the temperature was lowered to 40°C, and desalination was performed by a coagulation method using an aqueous naphthalene sulfonic acid 7-ormarin resin solution and a magnesium sulfate solution, and gelatin was added to reduce the pAg -31 2- 8,50, pH -5,85 seed crystal emulsion (A) at 16.9
I gained kg.

The obtained seed crystals were cooled and stored in a cool dark place.

Next, particles were grown using the seed crystal (A) in the following manner.

First, the following solutions were prepared. All amounts are per mole of silver halide.

Solution J (reaction mother liquor) Gelatin A 10 g Concentrated ammonia water 28 cc Glacial acetic acid 3 cc Water Liquid potassium bromide 5 g to make 600 cc Potassium iodide 3 g Gelatin A 0.8 g Water E liquid potassium bromide 90 g to make 110 cc Gelatin A 2.0 g Water M solution (0.75N') to finish 240cc AgN0. 9.9gNH
,OH7,0cc Water 110cc N liquid AgNOs' 130gNH,OH1
00cc water D liquid potassium bromide to make 240cc 94g water P liquid AgNOx to make 165cc 9.9gNH4OH7-
Occ water 110 cc of J solution was kept warm at 40°C and stirred at 800 rpm with a stirrer. The pH of Solution J was adjusted to 9.90 using acetic acid, and 62 g/1 mole of AgX of seed crystals (A) were collected and dispersed therein. Thereafter, P solution was added at a constant rate over 7 minutes to bring the pAg to 7.3. Furthermore, add 20% of K solution and M solution at the same time.
It was added over 34 minutes. I) Ag at this time was kept constant at 7.30 (Step 1). Further, using potassium bromide solution and acetic acid over 10 minutes I) H = 8.83, pAg =
After adjusting to 9.0, N solution and L solution were added simultaneously over 30 minutes. At this time, the inflow velocity ratio at the start of addition and at the end of addition was 1:10, and the flow velocity was increased with time. In addition, the pH was adjusted from 8.83 to 8.0 in proportion to the inflow amount.
It was lowered to 0. In addition, L liquid and N liquid accounted for 27% of the total
When the amount of 3 was added, O solution was additionally injected and added at a constant rate over 8 minutes. At this time, pAg is 9.0 to 11
．． It rose to 0 (Step 2). Further add acetic acid to p)I
was adjusted to 8.0. Next, excess salt was removed from this suspension by the desalting method shown below to obtain an emulsion. While keeping the suspension at 40°C, add the following compound I (5g/Ag
X l moO, Mg5o, (8g/AgX1 mo
ff) was added, stirred for 5 minutes, and left to stand still. Next, the supernatant liquid was drained to make a liquid volume of 200 cc per AgXlmo (2.
o12) was added and stirred for 5 minutes. Next, Mg5o, (
20 g/AgX1 mob) was added, stirred in the same manner as above, allowed to stand, and the supernatant was removed to perform desalting. Next, Ag
After gelatin a was added to disperse the X aggregates again, the mixture was stirred at 55° C. for 20 minutes and dispersed.

The resulting emulsion had monodisperse grains with an average grain size of 0.06 μm and a silver iodide content of about 2 mo1%.

Next, the obtained particles were chemically sensitized. That is, ammonium thiocyanate, chloroauric acid, and hypo were added to perform gold-sulfur sensitization.

Then 4-hydroxy-6-methyl-1,3,3a,
Add 7-chitrazaindene, then add Kl and spectral sensitizing dyes (a) and (b) at 300 mg and 5 mg/A, respectively.
gX l mof+ was added to perform spectral sensitization, and the resulting emulsion was designated as ■.

Next, prepare emulsions ■ to ■ in the same manner as for emulsion, except that the gelatin after the desalting process used in emulsion ■ is changed as shown below.
It was created.

Emulsion ■ Gelatin Mini Lime-processed gelatin made from cow bones α component content 35% Emulsion ■ Gelatin B: Lime-processed gelatin made from cow bones 35 36 Methods for increasing the α component described in the text ■～■ Created by combining α component content 43% Emulsion ■ Gelatin C: Gelatin α component content 48% obtained by treating gelatin B using an ultrafiltration membrane Emulsion ■ Gelatin d: Separating gelatin B using ethanol coacervation Content of α component in the intermediate fraction 59% Gelatins a and b were subjected to ion exchange treatment, and the calcium content of gelatins a and b was 500 ppm or less.

Spectral sensitizing dyes (a) (b) Next, apply the emulsion layer coating solution and the protective layer coating solution containing the obtained emulsions ■ to ■ onto both sides of the undercoated polyester film support. Two layers were coated simultaneously in the order of emulsion layer and protective layer, followed by drying to prepare a film.

The following additives and water-soluble polymers shown in Table 2 were added to the emulsion layer for AgX1mol12.

t-Butylcatechol 400mg Polyvinylpyrrolidone (molecular weight 10000) 1.0g
Trimethylolpropane 10g diethylene glycol 5g nitrophenylphosphonium chloride F 50n+g1.3-dihydroxybenzene-4 ammonium sulfonate 4g 2-mercaptobenzimidazole-578 sodium sulfonate 15mg cHx-COOCCH2)9CH.

CH, So3H CI(Coo(CH2)2cH(CHa)z■ 0sNa 7mg C,F,, -0-(CH2C)120←C)I2CH,
OH5,F, , SO, 2+ag B 1.1-dimethylol-1-bromo-l nitromethane
10 mg Styrene-maleic anhydride copolymer 7.5 g Snowtex N (manufactured by Nissan Corporation) 50 mg In addition, the following compounds were added to the protective layer per gelatin Ig.

Polymethyl methacrylate (matting agent) with an average particle size of 5 μm 7tmg (CL
= CH5o2CH! 070 g As the subtraction liquid, 50 vt% glycidyl methacrylate, 10 vt% methyl methacrylate, 40 vt% butyl methacrylate.
A copolymer consisting of three types of heptamers was prepared at a concentration of 10
A water-soluble copolymer dispersion was used by diluting it to vt%.

In addition, the unexposed film of the obtained sample, Zera 9- 40 The amount of tin was 3.10 g/m'' per side.

[Sensitometry] The standard light B described in "New Edition, Lighting Data Book" was used as a light source, and the film was exposed to the same amount of light on both sides with an exposure time of 0.1 seconds at 3.2 cm5 without a filter. The above sample was processed with XD-3R developer for 45 seconds using an SRX~501 automatic processor (manufactured by Konica Corporation).
The sensitivity of each sample was determined. Sensitivity is determined by calculating the reciprocal of the amount of light required to increase the blackening density by 1.0, and
It is expressed as relative sensitivity with the sensitivity of 100 as 100.

[Evaluation of Fixing Time] The time taken to complete fixing was measured using the following fixer. The fixer temperature was 25°C.

(Fixer) Ammonium thiosulfate 100g Sodium sulfite (anhydrous) 10IilI acid 8 Disodium ethylenediaminetetraacetate 0.05 Aluminum sulfate
7 sulfuric acid and glacial acetic acid water was added (pll was adjusted to 4.3). The results obtained are shown in Table 1.

2 5. Off 1 2 It also has excellent fixing properties.

Example 2 The sample obtained in Example 1 was processed using an automatic processor 5RX-501 (manufactured by Konica Corporation) to develop a developer XD-3R (manufactured by Konica Corporation) at 35°C and a fixer solution XF-SR (: ff, :force (
After passing through a fixed development and water washing process at 35°C (manufactured by Co., Ltd.), the film was squeezed and taken out just before entering the drying zone, and the following measurements were performed.

While blowing hot air onto the taken-out film using a commercially available dryer, the time until the surface temperature reached 30°C was measured using a surface thermometer.

The temperature of the washing water was 15°C.

Table 2 As shown in Table 2, it can be seen that the samples of the present invention are all superior in drying properties compared to the comparative samples.

〔Effect of the invention〕

According to the present invention, it was possible to obtain a silver halide photographic material having good fixing properties, excellent drying properties, high sensitivity, and high covering power. Furthermore, its effectiveness has made it possible to shorten the setting and drying steps during the manufacturing process and simplify the process.

[Brief explanation of drawings]

FIG. 1 is an example of gel chromatography showing the molecular weight distribution of gelatin according to the present invention: =43-44. Retention time (min) and absorption at 230 nm are shown.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material in which a photographic constituent layer consisting of at least one hydrophilic colloid layer is provided on both sides or one side of a support, the hydrophilic colloid layer has a molecular weight of about 100,000 as determined by separation by gel chromatography. 1. A silver halide photographic material comprising gelatin containing 40 wt% or more of an α component and a water-soluble polymer.