JPH04337724A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To suppress the occurrence of roller marks at the time of very rapid processing by incorporating chitosan into a silver halide emulsion layer. CONSTITUTION:This sensitive material with at least one silver halide emulsion layer and at least one nonphotosensitive layer on the base contains chitosan in the emulsion layer. Since chitosan is insoluble in water, in order to use chitosan after addition to an emulsion, chitosan is previously dissolved in an acid or used as a water-soluble chitosan salt formed with an acid such as acetic acid. Roller mark characteristics are improved and dryability fit for very rapid processing within 60sec can be enhanced.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material which can be processed at high speed. In particular, the present invention relates to a silver halide photographic material that has few roller marks even when subjected to ultra-rapid processing and has good drying properties.

0002

[Prior Art] In recent years, high-temperature, rapid processing has rapidly become popular in the development process of photographic light-sensitive materials (hereinafter referred to as "sensitive materials"), and even when processing various types of light-sensitive materials with automatic processors, the processing time has significantly decreased. It has been shortened. In order to achieve rapid processing, it is necessary to use a developer to achieve sufficient sensitivity in a short time, a photosensitive material that has excellent development progress and provides a sufficient degree of blackening in a short time, and dries in a short time after washing with water. Characteristics are required. A commonly used method for improving the drying properties of sensitive materials is to add a sufficient amount of hardener (gelatin crosslinking agent) in advance during the coating process of the sensitive material, and then perform development, fixing, and washing with water. There is a method of reducing the water content in the photosensitive material before drying starts by reducing the amount of swelling of the emulsion layer or hydrophilic colloid layer during the process. In this method, if a large amount of hardening agent is used, the drying time can be shortened accordingly, but as the amount of swelling decreases, development is delayed, resulting in low sensitivity, soft tone, and a decrease in covering power. This causes the inconvenience of doing so. Furthermore, even if the development progress is improved, the delay in fixing speed due to a high hardness film may cause silver halide to remain in the film after the development process, or hypo contained in the processing solution to remain in the film. This caused inconvenience and became an obstacle to reducing processing time.

On the other hand, methods for increasing the developing activity of the processing solution are also known, such as increasing the amount of the main agent or auxiliary developing agent in the developer, increasing the pH of the developer, and raising the processing temperature. . However, all of these methods have drawbacks such as impairing the stability of the processing solution, and even though the sensitivity is increased, the tone becomes softer and more likely to overlap. With the aim of improving the above-mentioned aspects, techniques using tabular grains have been proposed in U.S. Pat.
425 etc. Also, JP-A-63-305
343, and JP-A-1-77047 discloses a method for improving development progress and sensitivity/coverage ratio by controlling the development start point of silver halide grains having (111) planes to the apex and/or ridge of the grain and their vicinity. A technique for doing so has been disclosed. Furthermore, JP-A-58-111933 discloses that by using tabular grains and reducing the swelling of the hydrophilic colloid layer to 200% or less, it has a high covering power and does not require the addition of a dura during processing. A photographic element for graphics is disclosed. These known techniques are each excellent in improving the development progress of a photosensitive material, and have high utility value. However, if the processing time of each step of development, fixation, and water washing is shortened, not only the photographic sensitivity decreases, but also residual silver and residual hypo are deteriorated due to deterioration of fixability. These problems other than photographic properties can only be improved by modifying the silver halide grains, and must ultimately be solved by improving the binder. In other words, the thickness of the hydrophilic colloid layer controls the fixing, which becomes an obstacle to speeding up the fixing.

[0004] Regarding this point, Japanese Patent Application Laid-Open No. 64-7333
3, JP-A-64-86133, JP-A-1-105244
, JP-A-1-158436, etc., the amount of gelatin on the side having a hydrophilic colloid layer including a silver halide emulsion layer is set at 2.
A means is disclosed for achieving ultra-rapid processing in which the total processing time is 20 seconds or more and less than 60 seconds by adjusting the amount to a range of 0.00 to 3.50 g/m2 and combining it with other technical elements. Furthermore, JP-A-2-68537 discloses a method for achieving ultra-rapid processing by adjusting the weight ratio of silver to gelatin (silver/gelatin) in photosensitive silver halide coated on the emulsion layer to 1.5 or more. is disclosed. Furthermore, JP-A-63-2213
In No. 41, the silver halide grains in the emulsion layer mainly consist of tabular grains whose grain size is 5 times or more the grain thickness, the gelatin amount is 2.00 to 3.20 g/m2, and the melting time is A method is disclosed for achieving ultra-quick processing in which the total processing time is 20 seconds or more and less than 60 seconds by setting the time to 8 minutes or more and 45 minutes or less. As a result of examining these prior art techniques, the present inventors have confirmed that roller marks become significantly worse when the amount of gelatin is reduced or when the silver/gelatin ratio is increased while keeping the amount of coated silver constant. . Roller marks are a phenomenon in which when a photosensitive material is processed in an automatic processor, pressure is applied to the photosensitive material due to minute irregularities on the surface of a conveying roller, resulting in density unevenness in the form of black spots.

[0005]

Problems to be Solved by the Invention The problems to be solved by the present invention are, firstly, to provide a photosensitive material with improved roller mark characteristics; and secondly, to provide a photosensitive material with improved roller mark characteristics. The object of the present invention is to provide a sensitive material with improved drying properties and suitability for rapid processing.

[0006]

[Means for Solving the Problems] The above objects of the present invention have been achieved by the following method. That is, a silver halide photographic material comprising at least one silver halide emulsion layer and at least one non-photosensitive layer on a support, the emulsion layer containing chitosan.

The present invention will be explained in detail below. Gelatin is usually used as a protective colloid in the emulsion layer of a photosensitive material. In the present invention, the object of the present invention was achieved by adding chitosan as a part of this protective colloid. The chitosan of the present invention refers to poly-β(1,4)-D-glucosamine, which is normally used as a skeletal material of arthropods, molluscs, and fungi, and removes chitin, which is present in large amounts in nature. Obtained by acetylation. Usually, the deacetylation reaction is
It is carried out by alkali treatment of chitin, and chitosan with a degree of deacetylation ranging from 65% to 100% is commercially available as chitosan. The chitosan used in the present invention may have any degree of deacetylation as long as its water solubility is within a practical range. In addition, from the viewpoint of coating properties, the molecular weight of chitosan used in the present invention is such that the viscosity of a 0.5% solution thereof is preferably 500 cps.
Particularly preferably 100 cps or less. The chitosan used in the present invention is not limited to commercially available products, and chitosan separated and purified from a chitin source according to a known method or chitosan whose degree of deacetylation has been controlled may be used.

[0008] Chitosan is generally insoluble in water, and when used as a coating liquid, it is generally provided after being dissolved in an acid. In the present invention, since the chitosan salt is added to an emulsion, it is used by dissolving it in an acid, or a water-soluble chitosan salt is used which has been previously formed into a salt with an acid such as acetic acid. Acids used in the present invention include acetic acid, hydrochloric acid, nitric acid, glutamic acid,
Any acid that dissolves chitosan can be used, such as lactic acid, adipic acid, benzoic acid, phenylacetic acid, salicylic acid, aspartic acid, and p-aminobenzoic acid. These acids may be used alone or in an appropriate combination. This solution,
It is added to a silver halide emulsion for use in the present invention. There are no particular restrictions on the method or timing of addition, but it is preferably added after the emulsion is completed and before coating. The amount of chitosan solution added is not particularly limited, but is 2 to 50% by weight, preferably 10 to 50% by weight of the total binder amount forming the emulsion layer.
The effects of the present invention are exhibited within the range of 40% by weight.

[0009] Hydrophilic colloids other than chitosan can also be used in the emulsion layer, intermediate layer, and surface protective layer. There are no particular restrictions on the hydrophilic colloid to be added; for example, gelatin treated with alkali, acid, or enzyme treated, etc., made from bones and skins of cows, pigs, whales, fish, etc., can be used as raw materials. can. Further, gelatin modified by chemical modification, graft copolymerization, etc., gelatin modified by enzyme modification, etc., and gelatin graft copolymerized with vinyl monomer, etc. can be used. There is no particular restriction on the molecular weight of gelatin, and it can usually be used in the range of several hundred thousand to several thousand. In addition to gelatin, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate, dextran, and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, and polyvinyl alcohol. A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

The silver halide emulsion layer provided in the present invention is
In addition to hydrophilic colloids such as gelatin and chitosan, photosensitive silver halide, chemical sensitizers, spectral sensitizers, antifoggants, gelatin hardeners, film physical property improvers such as surfactants, and thickeners. , etc. can be contained. Regarding these,
Research Disclosure Magazine, Volume 176, 17643
(December 1978), etc. can be referred to. Next, the emulsion grains used in the present invention will be explained. The average particle size equivalent to a sphere with the same volume as the particles is 0.4μ
It is preferable that it is more than m. Especially 0.5-2.0μm
It is preferable that The narrower the particle size distribution, the better. The silver halide grains in the emulsion may have a regular crystal shape such as a cube or an octahedron, or may have an irregular crystal shape such as a spherical shape, a plate shape, a potato shape, etc. It may also have the following. It may also consist of a mixture of various crystal forms. The composition of the silver halide may be any of silver iodobromide, silver bromide, silver chlorobromide, and silver chloride. When a monodisperse emulsion is used as an emulsion in carrying out the present invention, the rate of addition of water-soluble silver salt and water-soluble halide may be increased in preparation of the monodisperse emulsion as the silver halide grains grow. desirable. By increasing the addition rate, the particle size distribution can be made more monodisperse and the mixing time can be shortened, which is advantageous for industrial production. It is also preferable in that the chance of formation of structural defects inside the silver halide grains is reduced. As a method for increasing the addition rate, as described in Japanese Patent Publication No. 48-36890, Japanese Patent Publication No. 52-16364, and Japanese Patent Application Laid-Open No. 55-142329, the addition rate of the silver salt aqueous solution and the halide aqueous solution can be continuously increased. or may be increased in stages. The upper limit of the above addition rate may be the flow rate just before new grains are generated, and the value depends on temperature, pH, pAg, degree of stirring, composition of silver halide grains, solubility, grain size, distance between grains, or protection. It varies depending on the type and concentration of colloid. Methods for producing monodisperse emulsions are known, for example, as described in J.
Photo. Sci. 12,242-251 (1
963), Special Publication No. 48-36890, No. 52-163
64 and Japanese Patent Application Laid-Open No. 55-142329, and the technique described in Japanese Patent Application Laid-Open No. 57-179835 can also be adopted. The silver halide emulsion used in the present invention may be a core-shell type monodisperse emulsion, and these core-shell emulsions are
No. 21 and the like. When a polydisperse emulsion is used as an emulsion in carrying out the present invention, a known method can be used for producing the polydisperse emulsion. For example, T. H
．． “The Theory ofth” by James
e Potographic Process” 4th
Edition, Macmillan Publishing (1977) 38-1
Apply methods such as the neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, controlled double jet method, conversion method, core/shell method, etc. described in literature such as page 04. It can be manufactured by

Further, tabular grains having a grain size of 5 times or more the grain thickness are preferably used for the present invention (in detail,
RESEARCH DISCLOSURE Volume 225
Item 22534 P. 20~P. 58, 1
Monthly issue, 1983, and JP-A No. 58-127921,
(described in Publication No. 58-113926). The tabular silver halide grains can be produced by appropriately combining methods known in the art. Tabular silver halide emulsions are produced by Cugnac and Chateau, Evolution of the Morphology of Silver Bromide Crystals during Physical Ripening.・
"Dueling Physical Lightning)" Science & Industry Photography, Volume 33,
No. (1962), pp. 121-125, Duffin, “Photographic Emulsion Chemistry”
emulsionchemistry)” Focal
Focal Press, New York, 1
966, p-66-p. 72, A. P. H. Trivelli, W. F. Smith
) Photographic Journal (Photogr
aphic Journal), vol. 80, p. 285 (1
940), etc.;
921, JP 58-113, 927, JP 58-1
No. 13,928 and US Pat. No. 4,439,520.

It is preferable to use a silver halide adsorbent substance in the silver halide emulsion. As a condition for adding the silver halide adsorptive substance, the temperature may be any temperature from 30°C to 80°C. Although the pH and pAg may be arbitrary, it is preferable that the pH is 6 to 10 and the pAg is 7 to 9 at the time of chemical sensitization. In the present invention, the silver halide adsorbing substance means a sensitizing dye or a photographic performance stabilizer. That is, azoles {e.g. benzothiazolium salts,
Benzimidazome salts, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.}; Mercapto compounds {e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptoimidazoles, mercapto Benzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptotriazines, etc.}; Thioketo compounds such as oxadorinthion; azaindenes { Known as antifoggants or stabilizers, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc. In addition, many compounds can be used as silver halide adsorbents. In addition, purines or nucleic acids, or
1-36213, JP-A-59-90844, and the like are also usable adsorbent substances.

As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holophoric cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. Useful sensitizing dyes for use in the present invention include, for example, U.S. Pat.
No. 052, No. 3,619,197, No. 3,713,8
No. 28, No. 3,615,643, No. 3,615,63
No. 2, No. 3,617,293, No. 3,628,964
No. 3,703,377, No. 3,666,480, No. 3,667,960, No. 3,679,428,
No. 3,672,897, No. 3,769,026, No. 3,556,800, No. 3,615,613, No. 3
, No. 615,638, No. 3,615,635, No. 3,
No. 705,809, No. 3,632,349, No. 3,6
No. 77,765, No. 3,770,449, No. 3,77
No. 0,440, No. 3,769,025, No. 3,745
, No. 014, No. 3,713,828, No. 3,567,
No. 458, No. 3,625,698, No. 2,526,6
No. 32, No. 2,503,776, Japanese Unexamined Patent Publication No. 48-765
No. 25, Belgian Patent No. 691,807, etc. Specific examples of sensitizing dyes are shown below.

[0014]

[Chemical formula 1]

The sensitizing dye used in the present invention may be added after chemical sensitization and before coating.

Methods for chemically sensitizing the silver halide emulsion used in the present invention include sulfur sensitization, selenium sensitization, reduction sensitization, and gold sensitization in the presence of the silver halide adsorbing substance described above. Known methods can be used, such as the method used alone or in combination. Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium. Specific examples include U.S. Patent No. 2,448,060 and British Patent No. 618,0.
It is described in No. 61, etc. In addition to the sulfur compounds contained in gelatin, sulfur sensitizers include various sulfur compounds such as thiosulfates, thioureas, thiazoles,
Rhodanines and the like can be used. Specific examples are U.S. Pat.
, No. 501,313 and No. 3,656,955. As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The photographic emulsion used in the present invention has been added to the chemical sensitization process of the present invention for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or to stabilize photographic performance. Various compounds can be contained in addition to the silver halide adsorptive substance. Namely, azoles {e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.}; mercapto compounds {e.g. mercapto thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc.}; thioketo compounds such as oxadorinthion; azaindenes {e.g. triazaindenes, Tetraazaindenes (especially 4
-Hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.}; Known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds can be added.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain various surfactants. For example, saponins (steroids),
Nonionic surfactants such as alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene oxide adducts of silicones), alkyl esters of sugars, etc. agents; alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, etc. Anionic surfactants; amphoteric surfactants such as alkylbetaines and alkylsulfobetaines; cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, pyridinium salts, and imidazolium salts can be used. Among these, saponin, dodecylbenzenesulfonic acid Na salt, di-2-ethylhexyl α-sulfosuccinic acid Na salt, p-octylphenoxyethoxyethanesulfonic acid Na salt, dodecyl sulfate Na salt, triisopropylnaphthalenesulfonic acid Na salt, N- Anions such as methyl-oleoyl taurine Na salt, dodecyltrimethylammonium chloride, N-oleoyl-N'-N'-N
'-Trimethylammoniodiaminopropane bromide, cations such as dodecylpyridium chloride, N-
Dodecyl-N,N-dimethylcarboxybetaine, N-
Betaines such as oleyl-N,N-dimethylsulfobutylbetaine, poly(average degree of polymerization n=10) oxyethylene cetyl ether, poly(n=25) oxyethylene p
-nonylphenol ether, bis(1-poly(n=1
5) Nonions such as oxyethylene-oxy-2,4-di-t-pentylphenyl)ethane can be particularly preferably used. As the antistatic agent, perfluorooctanesulfonic acid K salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N
-perfluorooctanesulfonylaminoethyloxypoly(n=3)oxyethylenebutanesulfonic acid Na salt, N-perfluorooctanesulfonyl-N',N',
N'-trimethylammoniodiaminopropane chloride, N-perfluorodecanoylaminopropyl-N'
, N'-dimethyl-N'-carboxybetaine, fluorine-containing surfactants, JP-A-60-80848, JP-A-60-80848, JP-A-61.
-112144, 62-172343, 62-
Nonionic surfactants, alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or composite oxides obtained by doping these with antimony or the like can be preferably used.

In the present invention, as matting agents, US Pat.
Using homopolymers of polymethyl methacrylate or copolymers of methyl methacrylate and methacrylic acid as described in No. 94 and No. 4,396,706, organic compounds such as starch, and fine particles of inorganic compounds such as silica, titanium dioxide, sulfuric acid, and barium strontium. Can be done. The particle size is 1.0 to 10 μm, especially 2 to 5 μm.
It is preferable that The surface layer of the photographic light-sensitive material of the present invention contains a lubricant as disclosed in US Pat. No. 3,489,576 and US Pat.
Silicone compounds described in No. 047958 etc., Japanese Patent Publication No. 1973
In addition to the colloidal silica described in JP 6-23139, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used. The hydrophilic colloid layer of the photographic material of the present invention contains trimethylolpropane, pentanediol, butanediol, ethylene glycol,
Polyols such as glycerin can be used as plasticizers.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-[
β-(vinylsulfonyl)propionamide], etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazine, etc. Nylated gelatin and the like can be used alone or in combination. Among them, JP-A-53-4122
1, 53-57257, 59-162546, 6
The active vinyl compounds described in US Pat. No. 0-80846 and the active halides described in US Pat. No. 3,325,287 are preferred. Polymer hardeners can also be effectively used as hardeners in the present invention. Examples of the polymeric hardening agent used in the present invention include dialdehyde starch, polyacrolein, polymers having aldehyde groups such as the acrolein copolymer described in U.S. Pat. No. 3,396,029, and U.S. Pat.
Polymers having epoxy groups described in No. 23,878, polymers having dichlorotriazine groups described in U.S. Patent No. 3,362,827, Research Disclosure Magazine 17333 (1978), etc., JP-A-56
-66841, a polymer having an active ester group, JP-A-56-142524, U.S. Patent No. 4,
161,407, JP-A-54-65033, Research Disclosure Magazine 16725 (1978), etc., examples include polymers having an active vinyl group or a group that is a precursor thereof, and active vinyl groups,
Alternatively, a polymer having a group that is a precursor thereof is preferable, and among them, an active vinyl group or a group that is a precursor thereof is bonded to the polymer main chain by a long spacer as described in JP-A-56-142524. Particularly preferred are such polymers. The hydrophilic colloid layer in the photographic light-sensitive material of the present invention is preferably hardened with such a hardening agent so that the swelling ratio in water is 280% or less, particularly 200 to 280%.

The emulsion layer of the photographic material of the present invention may contain a plasticizer such as a polymer or an emulsion in order to improve pressure characteristics. For example, British Patent No. 738,61
U.S. Patent No. 8 contains heterocyclic cyclic compounds, U.S. Patent No. 738,637 contains alkyl phthalates, U.S. Pat. No. 121,060 discloses a method using carboxyalkylcellulose, JP-A No. 49-5017 discloses a method using paraffin and a carboxylic acid salt, and JP-B No. 53-28086 discloses a method using an alkyl acrylate and an organic acid.

A polyethylene terephthalate film is preferred as the support. In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support is preferably subjected to corona discharge treatment, glow discharge treatment, or ultraviolet irradiation treatment, or is made of styrene-butadiene-based latex, vinylidene chloride-based latex, etc. An undercoat layer may be provided, and a gelatin layer may be further provided on top of the undercoat layer. Further, an undercoat layer may be provided using an organic solvent containing a polyester swelling agent and gelatin. These undercoat layers can be surface-treated to further improve their adhesion to the hydrophilic colloid layer. EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

[0023]

[Example] Example 1 (Preparation of emulsion A-1) 4 potassium bromide in 1 liter of water
．． 5g, gelatin 20.6g, thioether HO (CH
2) Add 2.5 cc of 5% aqueous solution of 2S(CH2)2S(CH2)2OH, and add 37 cc of silver nitrate aqueous solution (3.43 g of silver nitrate) and 2.97 g of potassium bromide into a container kept at 60°C while stirring. 33 cc of an aqueous solution containing 0.363 g of potassium iodide was added by a double jet method. Next, after adding an aqueous solution of 0.9 g of potassium bromide, 70°C
53cc of silver nitrate solution (4.90g of silver nitrate)
was added over 13 minutes. Here, 15 cc of an ammonia aqueous solution of 255 was added, and after physical ripening for 20 minutes at the same temperature, 14 cc of a 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by a controlled double jet method while maintaining a pAg of 8.5 g. Next, add 10 cc of 2N potassium thiocyanate solution and A of 0.07 μm in diameter.
gI fine particles were added in an amount of 0.05 mol % based on the total amount of silver. After physical ripening at the same temperature for 5 minutes, the temperature was lowered to 35°C. Thus, the total silver iodide content was 0.31 mol%
, average projected area diameter 1.10μm, thickness 0.165μm
, monodisperse tabular grains with a diameter variation coefficient of 18.5% were obtained. After this, soluble salts were removed by a sedimentation method. 4 again
Raise the temperature to 0℃ and add 30g of gelatin and 2 phenoxyethanol.
．． 35 g and 0.8 g of sodium polystyrene sulfonate as a thickener, and with caustic soda and silver nitrate solution,
The pH was adjusted to 5.90pAg8.25. This emulsion was subjected to chemical sensitization while being stirred and maintained at 56°C. First, 0.043 mg of thiourea dioxide was added and held for 22 minutes to perform reduction sensitization. Next, 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 500 mg of sensitizing dye I-1 were added. Next, 3.3 mg of sodium thiosulfate and 2.6 mg of chloroauric acid.
was added and cooled to 35° C. after 40 minutes. In this way, preparation of emulsion A-1 was completed.

Preparation of chitosan solution Chitosan used was Fronac C manufactured by Kyowa Yushi Kogyo Co., Ltd. 70g of Fronac C and 650g of distilled water, 1N
A 7% chitosan solution was prepared by dissolving it in 280 g of hydrochloric acid.

Preparation of Coating Sample The following chemicals were added per mole of silver halide of the A-1 emulsion to prepare a coating solution.・2,6-bis(hydroxyamino)-4-diethylamino-1,3,5-triazine
72mg
・Gelatin Total with gelatin used in the surface protective layer described below
The amount was added so that the coating amount would be the value shown in Table 1. - Chitosan solution The amount of coating was added as shown in Table 1.・Trimethylolpropane
9g Sodium polystyrene sulfonate
0.6 g Hardener 1,2-bis(vinylsulfonylacetamido)ethane Swelling in pure water was adjusted to the values shown in Table 1.

[0026]

[Case 2]

Preparation of surface protective layer coating solution The surface protective layer was prepared so that each component was coated in the following amounts. Contents of surface protective layer/gelatin
0.966
g/m2・Sodium polyacrylate
0.023
g/m2 (average molecular weight 400,000) ・4-hydroxy-6-methyl-1,3,3a,7
-tetrazaindene
0.015 g/m2

[0028]

[Chemical formula 3]

・Polymethyl methacrylate
0.087 g/m2
(Average particle size 3.7μm) ・Proxel
0.0005
g/m2 (adjusted to pH 7.4 with NaOH)

Preparation of Support (1) Preparation of Dyes for Undercoat Layer The following dyes were ball milled by the method described in JP-A-63-197943.

[0031]

[C4]

434 ml of water and Triton X-2
6.7% aqueous solution of 00 surfactant (TX-200) 79
1 ml was placed in a 2 liter ball mill. dye 20
g was added to this solution. Zirconium oxide beads 4
00 ml (2 mm diameter) was added and the contents were ground for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the zirconium oxide beads were removed by filtration. When the obtained dye dispersion was observed, the particle size of the pulverized dye had a wide distribution ranging from 0.05 to 1.15 μm in diameter, and the average particle size was 0.37 μm. Furthermore, by performing centrifugal scanning, dye molecules with a size of 0.9 μm or more were removed. In this way, dye dispersion D-1 was obtained.

(2) Preparation of support A biaxially stretched polyethylene terephthalate film with a thickness of 183 μm was subjected to corona discharge treatment, and a first coating solution having the composition shown below was applied in an amount of 5.1 cc. It was applied using a wire bar coater and dried at 175°C for 1 minute. Next, a first undercoat layer was provided on the opposite side in the same manner. The polyethylene terephthalate used contained 0.04 wt% of a dye having the following structure.

[0034]

[C5]

・Butadiene-styrene copolymer latex solution (
Solid content 40%, butadiene-styrene weight ratio = 31/6
9)

79 cc・2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% aqueous solution

20.5cc/distilled water

900.5cc*The latex solution contains 0.4wt of the following compound as an emulsifying dispersant based on the latex solid content.
% contained.

[0036]

[C6]

[0037] On the first undercoat layer on both sides, a second undercoat layer having the composition shown below is coated on each side at 150° C. using a wire bar coater method in an amount as described below.・Dry. ·gelatin

160g/m2・Dye dispersion D-1 (26mg/m2 as dye solid content)

[0038]

[Chemical 7]

- Matting agent Polymethyl methacrylate with an average particle size of 5 μm

2.5mg/m2

Preparation of Photographic Material The emulsion layer and surface protective layer were coated on one side of the prepared support by coextrusion. The amount of silver coated per side is 1
．． It was set to 75g/m2. The swelling ratio determined by the amount of coated gelatin and the freeze-drying method using liquid nitrogen was adjusted by adjusting the amount of gelatin and hardener added to the emulsion layer and set as shown in Table 1. Photographic materials 1 to 6 were thus obtained.

(Evaluation of roller marks) Photographic materials 1 to 6
Cut into 30.5cm x 25.4cm, color temperature 540
Exposure was performed from one side with a 0°K light source. At this time,
By increasing or decreasing the exposure time, the density in the roller mark evaluation process was adjusted to be uniformly 1.0 including the base density. Roller marks in the form of black spots observed on the photosensitive material thus processed were evaluated. The evaluation criteria were based on the following sensory evaluation. ◎ … There are almost no roller marks. ○ … There are slight roller marks, but they are not noticeable. △ … There are roller marks, but they are acceptable for practical purposes. × … There are many roller marks and uneven density. Not allowed in large quantities

<Developer> Potassium sulfite

40 g Trisodium hydroxyethylethylenediaminetriacetate 8
g 1,4-dihydroxybenzene

28 g boric acid

10
g 5-methylbenzotriazole

0.04g 1-phenyl-5-mercaptotetrazole 0
．． 01g Sodium metabisulfite

5 g acetic acid (90%)

13g
triethylene glycol
1
5 g 1-phenyl-3-pyrazolidone
1.2 g S-nitroindazole

0.2 g glutaraldehyde
2
g

[0043]

[Chemical formula 8]

Disodium ethylenediaminetetraacetate
2.0
g potassium bromide

4.0 g 5-nitrobenzimidazole
Make 1.0 g or more into a 1 liter aqueous solution and adjust the pH to 10.50 with potassium hydroxide <Fixer> Sodium thiosulfate pentahydrate
45
g Ethylenediaminetetraacetic acid disodium
0.5 g ammonium thiosulfate

150 g anhydrous sodium sulfite
8g
potassium acetate

16 g aluminum sulfate 10
~18 hydrate salt
27 g sulfuric acid (50w
t%)
6
g citric acid

1 g boric acid


7 g glacial acetic acid

5
Make 1 liter of the above into an aqueous solution and adjust the pH to 4.0 with glacial acetic acid.

The processing temperatures of the developer and fixer were as follows. Development: 35°C Fixing: 33°C Washing: 25°C Drying: 45°C As an automatic developing machine, R manufactured by Fuji Photo Film Co., Ltd.
N-type was used, and the DrytoDry treatment time was 90 seconds.

[Evaluation of drying property] <Developer concentrate> Potassium hydroxide

56.6 g Sodium sulfite

200 g diethylenetriaminepentaacetic acid
6.7 g
potassium carbonate

16.7 g boric acid

10
g Hydroquinone

83.3 g diethylene glycol
40g
4-hydroxymethyl-4-methyl-1-phenyl-3
− Pyrazolidone

22.0 g 5-methylbenzotriazole
2 g water 1
liter (adjust to pH 10.60). <Fixer concentrate> Ammonium thiosulfate
56
0 g sodium sulfite

60 g Ethylenediaminetetraacetic acid disodium dihydrate
0.10g sodium hydroxide

24g
Make up to 1 liter with water (adjust to pH 5.10 with acetic acid). When starting the developing process, each tank of the automatic developing machine was filled with a processing solution having the following composition. Developing tank: 333 ml of the above developer concentrate, 667 ml of water, and 10 ml of a starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to 10.25. Fixing tank: 200 ml of the above-mentioned fixer concentrate and 800 ml of water The automatic developing machine was an FPM9000 manufactured by Fuji Photo Film Co., Ltd., which was modified to increase the film conveyance speed, and the Dry to D
The processing time for ry was 30 seconds. Washing water was allowed to flow at a rate of 3 liters per minute only while the film was passing through, and was stopped at the rest of the time. The replenishment of the developer and fixer and the processing temperature were as follows.

[0047] Under the above conditions, each photographic material cut into four pieces was processed continuously, and the drying properties of the film were sensory evaluated by touch. The film was processed continuously with the short side facing the transport direction. The results are summarized in Table-1. ◎ Even after the 30th sheet, the film comes out warm and dry. No problem at all. ○ Even at the 30th sheet, the film is completely dry. The temperature when touched was similar to that of the film left at room temperature. △ At the 30th sheet, the film is a little cold, but the film that has been continuously processed does not stick to each other and is at a practically acceptable level. Film comrades glue together
.

[Method for measuring swelling ratio] The swelling ratio in water in the present invention is measured by a freeze-drying method. That is, the swelling ratio of the hydrophilic colloid layer is measured after the photographic material has been aged for 7 days at 25° C. and 60% RH. Dry film thickness (a
) is determined by scanning electron microscopy of sections. Swelling film thickness (
b) is determined by immersing the photographic material in distilled water at 21° C. for 3 minutes, freezing it in liquid nitrogen, and then observing it with a scanning electron microscope. The swelling rate is determined by dividing the value of ((b)-(a)) by the value of (a) and multiplying it by 100 (%). The results are summarized in Table 1.

[0049]

[Table 1]

Among the results shown in Table 1, photographic material 1 had inferior roller marks and was not at a practical level. In addition, photographic materials 2 and 3 had poor drying properties, and when subjected to ultra-rapid processing,
Not practical. However, 0.3g/chitosan
Photographic material 4 containing m2, 0.5g/m2, 0.7g/m2
, 5 and 6, there are almost no roller marks,
The effects of the present invention are obvious.

[0051]

Effects of the Invention: A silver halide photographic material of the present invention containing chitosan in the emulsion layer, which has improved roller marks that occur when processed in an automatic processor and is suitable for ultra-rapid processing. We were able to provide the following.

[Chemical formula 9]

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

[Table 2]

[Table 3]

Claims (1)

[Claims] Claim 1. A silver halide photographic material comprising at least one silver halide emulsion layer and at least one non-light-sensitive layer on a support, characterized in that the emulsion layer contains chitosan. Silver chemical photographic material.