JPH04179946A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To accelerate drying by incorporating a specified amt. of at least one kind of water-soluble oligomer into a hydrophilic colloidal layer and carrying out processing under specified conditions. CONSTITUTION:At least one kind of water-soluble oligomer is incorporated into at least one hydrophilic colloidal layer of a silver halide photographic sensitive material with the layer on the base by 10-50% of the total weight of the layer and the sensitive material is imagewise exposed and processed with a roller conveyance type automatic processing machine under conditions satisfying and equation l<0.75>XT=50 to 125 [where l is the length (m) of the sensitive material to be processed, 0.7<l<4.0 and T is the time (sec) required to pass the length (l)]. Even in the case of rapid processing with the automatic processing machine, the occurrence of roller marks is suppressed and drying can be accelerated.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, the present invention relates to a silver halide photographic light-sensitive material, and more specifically, a halogen silver halide photographic material that has rapid developability, suppresses the occurrence of roller marks, and has improved drying properties. This invention relates to silver oxide photographic materials.

[Background of the invention]

In recent years, processing times for silver halide photographic materials have been becoming faster in response to user needs as film consumption has increased, and medical photosensitive materials are no exception.

Manufacturers are trying to improve developability by using the silver halide composition of the photosensitive material itself and development accelerators, and by making the developer composition and processing conditions more active. Efforts are being made.

However, one of the biggest problems that arises as a result of speeding up processing is the drying properties of photosensitive materials after processing. That is, because the processing time is short, the processing is completed without sufficient drying, resulting in scratches, scratches, and scratches.

Various proposals have been made in the past to address these problems, and in order to improve drying properties, there are methods to reduce the water absorption of photosensitive materials, such as methods to increase the degree of hardening of gelatin films, or direct methods. A known technique is to reduce water absorption by reducing the binder component, ie, gelatin, in the silver halide emulsion layer or backing layer.

However, these conventional techniques have not been very effective in meeting the recent ultra-quick processing requirements.

In addition, the gelatin reduction method for the silver halide emulsion layer causes photographic properties such as increased fog or deterioration of graininess.
Furthermore, resistance to scratches and the like deteriorates. Also, reducing the amount of gelatin in the backing layer is not at all desirable, for example, making it impossible to maintain a well-balanced curling (curving toward the emulsion side or the opposite side) of the film. This results in an inviting result.

On the other hand, automatic processors generally consist of a developing tank, a stop tank, a fixing tank, a washing tank, a drying zone, etc., and the exposed film is quickly conveyed by many rollers used in these tanks.

Therefore, the film is susceptible to roller marks caused by roller pressure or fluid pressure marks caused by the developer, and in the case of X-ray film, there is a risk that these phenomena may lead to misdiagnosis on the image.

As described above, in order to advance rapid processing, there are many problems on the photosensitive material side, and a new technology to solve them has been strongly desired.

[Purpose of the invention]

Accordingly, the first object of the present invention is to provide a silver halide photographic material that dries quickly in rapid development processing. A second object of the present invention is to relate to a silver halide photographic material that does not generate roller marks during rapid processing. Other objectives will become apparent from the description below.

[Structure of the invention]

The above object of the present invention has been achieved by discovering that the above object can be achieved by the following method.

- That is, in a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, at least one selected from water-soluble oligomers is added to the hydrophilic colloid layer based on the total weight of the hydrophilic colloid layer. 10% or more of 50
% or less, and which is processed after imagewise exposure in a roller conveyance type automatic processor under the conditions expressed by the following formula [A].

(A) Qo”x T = 50~125 (0
, 7<J<4.0) where a represents the processing length (unit 2 recommended) when processing the photosensitive material, and T represents the time required to pass through a (unit 2 seconds).

The present invention will be explained in detail below.

In the present invention, the term "water-soluble oligomer" refers to an oligomer that is soluble in water, although it does not necessarily have to have a high solubility in water.

For example, 0.05g for 100g of water at 20℃
It is sufficient that it dissolves in an amount of at least 0.1 g, preferably 0.1 g or more. The higher the solubility of the water-soluble oligomer in the developer or fixer, the more preferable it is, and the more preferably the solubility is 0.05 or more, more preferably 0.5g or more per 100g of developer. Particularly preferred are those having a solubility of 18 or more.

In the present invention, oligomer refers to a low molecular weight polymer having a degree of polymerization of about 10 to about 14 and a molecular weight of about 20.0 to about 0.

By incorporating the water-soluble oligomer according to the present invention into the hydrophilic colloid layer of a silver halide photographic light-sensitive material, sufficient drying properties can be obtained in a short period of time in rapid processing since the water retention capacity is smaller than that of gelatin. becomes possible. Furthermore, it has surprisingly been found that resistance to roller marks from automatic processing machines is also improved.

Water-soluble oligomers may be natural or synthetic.

Among the water-soluble oligomers that can be used in the present invention, synthetic water-soluble oligomers include those having, for example, nonionic groups, anionic groups, and both nonionic and anionic groups in their molecular structures. can be mentioned. Examples of nonionic groups include ether groups, ethylene oxide groups, and hydroxy groups. 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 oligomer 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.

Examples of natural water-soluble oligomers include those having, for example, nonionic groups, anionic groups, and both nonionic and anionic groups in their molecular structures.

Preferred water-soluble oligomers include those containing repeating units of the following general formula CI), particularly those containing 10 to 100 mol % of this in one polymer molecule.

These synthetic water-soluble oligomers are known compounds such as West German Patent Application (0LS) No. 2,312,708, U.S. Pat. No. 3,620.751, U.S. Pat.
No. 5, Japanese Patent Publication No. 43-7561, etc., or a method analogous thereto.

General formula CI) 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 (including those having a substituent, for example, a methyl group, an ethyl group) , propyl group, butyl group, etc.), a halogen atom, or -〇〇, C00M'.

L is -CONH-1-Nl(CO-1-COO-1-O
Represents CO-1-CO-1 or -〇-.

J is an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms (including those having substituents).

For example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc., and those with substituents), arylene group (including those with substituents; for example, phenylene group, etc.) represents an aralkylene group (including those having a substituent; for example, υn represents an integer from O to 4).

Further, Q represents a hydrogen atom or R3, where Ml and Ml represent a hydrogen atom or a cationic group, and R9 represents an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group). or those with substituents), and R3, R
4, Rfi, R@, R7 and R@ are hydrogen atoms,
Alkyl groups having 1 to 20 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, hexadecyl group, etc., or those with substituents thereof),
Alkenyl groups (e.g., vinyl groups, aryl groups, etc., or those with substituents thereof), phenyl groups (e.g., phenyl groups, methoxyphenyl groups, chlorophenyl groups, etc., or those with these substituents), aralkyl groups (e.g., benzyl group, etc. or those with substituents),
X represents an anion, and p and q each represent 0 or l.

Y represents a hydrogen atom or ÷L←→J÷--Q.

The synthetic water-soluble monomer constituting the unit represented by general formula (I) can be copolymerized with an ethylenically unsaturated monomer. Examples of copolymerizable ethylenically unsaturated monomers include styrene, alkylstyrene, hydroxyalkylstyrene (the alkyl group preferably has 1 to 4 carbon atoms, such as methyl, ethyl, butyl, etc.), vinylbenzenesulfonic acid, and its like. salts, a-methylstyrene, 4-vinylpyridine, N-vinylpyrrolidone, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, vinyl propionate, etc.), ethylenically unsaturated monocarboxylic or dicarboxylic acids and its salts (e.g. acrylic acid,
methacrylic acid), maleic anhydride, esters of ethylenically unsaturated molar carboxylic or dicarboxylic acids (for example n-butyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate), and the like.

Next, specific examples of synthetic water-soluble oligomers having repeating units of general formula [I] will be illustrated, but the present invention is of course not limited thereto.

The numerical value in parentheses is the average molecular weight Mn.

CH.

(9.000) ■ -16 (However, nl: nz = 30 mol% near 0 mol%, Mn
= approx. 2.600) ■ -18 (2,100) I -20 ■-22 ■ -23 CH.

SO, Na (2,150) When the above synthetic water-soluble oligomer is used, it preferably has a molecular weight of 1.000 to 20,000, more preferably 3,000 or less.

Next, natural water-soluble polymers that can be used in the present invention include those described in detail in the Comprehensive Technical Data Collection of Water-Soluble Polymer Water-Dispersible Resins (published by Management Development Center Publishing Department). In particular, lignin, starch, pullulan, cellulose, alginic acid, dextran, dextrin, guar gum, gum arabic, pectin, casein, agar, xanthanzam, cyclodextrin, locust bean gum, tragacanth gum, carrageenan, glycogen, laminaran, lignin, nigeran, etc. and derivatives thereof are preferred.

Derivatives of natural water-soluble oligomers include sulfonated,
Carboxylated, phosphorylated, sulfoalkylenated, or carboxyalkylenated, alkyl phosphorylated,
and its salts, polyoxyalkylenes (e.g. ethylene,
Preferred are glycerol, propylene, etc.) and alkylation (methyl, ethyl, benzylation, etc.).

Among natural water-soluble oligomers, glycose polymers and derivatives thereof are preferred, and among glycose polymers and derivatives thereof, starch, glycogen, cellulose, lignin, dextran, nigeran, etc. are preferred, and dextran and derivatives thereof are particularly preferred. preferable.

Dextran is a polymer of a-1,6-linked D-glyose, and is generally obtained by culturing dextran-producing bacteria in the presence of saccharides. It can be obtained by reacting isolated dextran sucrase with saccharides. In addition, these native dextrans are reduced to a desired molecular weight by a partial decomposition polymerization method using acid or alkaline enzymes, and the intrinsic viscosity is reduced to 0.0.
3 to 2.5 can be obtained.

Examples of modified dextran include dextran sulfate, carboxyalkyldextran, and hydroxyalkyldextran.

The molecular weight of these natural water-soluble oligomers is 1.000~
20,000 is preferred, particularly 3000
It is as follows.

Methods for producing these dextrans and their derivatives are described in Japanese Patent Publication No. 35-11989 and U.S. Patent No. 3,762.
, No. 924, Special Publication No. 45-12820, No. 45-1
No. 8418, No. 45-40149, No. 46-3119
It is stated in No. 2.

In the present invention, the synthetic or natural water-soluble oligomer is preferably contained in the hydrophilic colloid layer in an amount of 10% or more, more preferably 10% or more and 50% or less of the total weight thereof. . The addition time may be any step before coating the hydrophilic colloid layer.

The hydrophilic colloid layer in the present invention refers to a layer adjacent to an emulsion layer such as a photosensitive or substantially non-photosensitive silver halide emulsion layer, a protective layer, an intermediate layer, and an undercoat layer. .

The present invention is applicable to all silver halide photographic materials, but is particularly suitable for high-sensitivity black and white photographic materials.

The silver halide photographic material according to the present invention can be developed by a commonly used known method.

The developer is a commonly used developer, such as hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-p
-Aminophenol or p-7 22-diamine may be used alone or in combination of two or more thereof, and other commonly used additives may be used.

Developers containing aldehyde hardeners can also be used in the silver halide photosensitive material of the present invention, such as dialdehydes such as maleic dialdehyde, glutaraldehyde and their sodium bisulfite salts, etc. It is also possible to use a developer known in the photographic field containing .

Next, conditions under which the photosensitive material of the present invention is processed will be described.

Q, which is the processing length when processing the photosensitive material of the present invention, is 0
．． The range is more than 7 and less than 4.0 (unit: l). a
If it is less than 0.7, each processing step becomes smaller and the sensitivity may decrease. Also, if it is applied to a device that uses rollers to transport photosensitive materials, the number of rollers used will become smaller, resulting in poor transportability. becomes worse. On the other hand, when Q is 4.0 or more, the conveyance speed becomes too high and scratches are likely to appear on the film.

Further, the product of 10.7S and T is 50 or more and 125 or less.

If this value is less than 50, the sensitivity of the photosensitive material may decrease or color retention may become a problem.

More preferably, the product of Q076 and T is 76 or more.

On the other hand, when the product of Qo, 71 and T exceeds 125, the graininess of the photographic image deteriorates and fog increases, although the sensitivity hardly increases.

When processing using an automatic developing machine, it is preferable to use a roller conveyance type automatic developing machine, and in this case, the total number of conveying rollers is 0. It is preferable that it is in the range of O1 to 0.04. Further, the time for multiple treatment areas is preferably within the following range.

10 times of insertion, 10 times of development, 10 times of 25-40% fixing
12-25% Wash with water for 10 minutes 10-25% Squeeze + dry 25-45% total
The roller used 100% has a diameter of 12m + + + + ~ 60mm at the conveying part and a length of 30C! It is preferably between 1-110 cm, and various materials can be used. For example, Bakelite-based materials (which may contain glass powder, metal powder, and plastic powder) or rubber-based materials are used for the developing, fixing, washing, and drying parts. (neoprene, isoprene, silicone rubber, etc.) can be used. The transition and squeeze parts are made of water-repellent and elastic silicone rubber, or synthetic leather with high water absorption.
It is preferable to use "CLARINO" (manufactured by Kuraray Co., Ltd.).

It should be noted that appropriate processing liquids such as a developer and a fixer can be used during processing depending on the photosensitive material.

Note that 1 in FIGS. 1 and 2 is the 10th part of the photosensitive material insertion slot.
2 is the final roller at the drying outlet, 3a is the developing tank, 36 is the fixing tank, 3c is the washing tank, 4 is the photosensitive material to be processed, 5 is the squeeze part, 6 is the drying part, and 7 is the drying air. Shows the air outlet.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be any silver halide such as silver iodobromide, silver iodochloride, silver iodochlorobromide, etc., but it is said that particularly high sensitivity can be obtained. From this point of view, silver iodobromide is preferred.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
It may be a completely isotropic crystal like a tetrahedron, a polyhedral crystal like a sphere, a twin crystal with planar defects, or a mixed or composite type thereof. Good too. The grain size of these silver halide grains may range from fine grains of 0.1 .mu.m or less to large grains of up to 20 .mu.m.

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 (1978
1 emulsion manufacturing method (December 2013) on pages 22-23
onPreparation and type, es)
and (RD) No. 18716 (November 1979), p. 648.

The emulsion of the silver halide photographic light-sensitive material according to the present invention is described, for example, in "The theory o" by T. H. James.
f thephotographic process
"4th edition, published by Macmillan (1977)"
Methods described on pages 38-104, G.F., Dauffin
Author: “Photographic Emulsion Chemistry” “Photographic e
+aulsionChe+aistry”, Focal
Press (1966), Glafkid, P.
“Physics and Chemistry of Photography” by Chimie etphy
sique photography” Pau
l Monte1 (1967), V, L, Ze
“Manufacture and Coating of Photographic Emulsions” by likman et al. “Mak
ing and coating photograp
It is prepared by the method described in "Hices+ulsion" published by Focal press (1964).

That is, solution conditions such as neutral method, acidic method, ammonia method, etc.
It can be produced using mixing conditions such as forward mixing method, back mixing method, double jet method, Chondral double jet method, etc., particle preparation conditions such as conversion method, core/shell method, and combination methods thereof.

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

Examples of silver halide emulsions preferably used in the present invention include JP-A-59-177535 and JP-A-61-802.
No. 237, No. 61-132943, No. 63-4975
1 and Japanese Patent Application No. 63-238225. The convex walls of the crystal are cubic, tetradecahedral, octahedral, and the intermediate (1, 1,
1) plane and (1,0,0) plane may be arbitrarily mixed.

The term "monodispersed emulsion" as used herein means at least 9 particles in number or weight when the average particle diameter is measured by a conventional method, for example.
5% of the grains are silver halide grains within ±40%, preferably within ±30% of the average grain size. 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 a core/shell type monodisperse emulsion having a clear two-layer structure consisting of a high iodine core portion and a low iodine shell layer.

The silver iodide content of the high iodide part is 20 to 40 mol%, particularly preferably 20 to 30 mol%, which is alkali.

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, US Patent No. 3,574.62
It is described in publications such as No. 8 and No. 3,655.394.

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. In addition, as a method for obtaining a core/shell emulsion, for example, British Patent 1
, 027,146, U.S. Pat. No. 3,505,068,
This is described in detail in publications such as No. 4,444.877 and Japanese Unexamined Patent Publication No. 60.14331.

The silver halide emulsion used in the present invention may be tabular grains having an aspect ratio of 4 or more and less than 30.

The advantages of such tabular grains include improved spectral sensitization efficiency, improved graininess and sharpness of images, etc., as described in British Patent No. 2,112.157 and US Patent No. 4,4.
No. 39.520, No. 4,433,048, No. 4,41
No. 4,310, No. 4,434.226, Japanese Unexamined Patent Publication No. 1983-
No. 113927, No. 58-127921, No. 63-1
No. 38342, No. 63-284272, No. 63-30
It can be prepared by the method described in publications such as No. 5343.

The above-mentioned emulsions may be of the surface latent image type that forms a latent image on the grain surface, the internal latent image type that forms the latent image inside the grain, or the emulsion type that forms the latent image on the surface and inside the grain. Good too. These emulsions may use 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. at the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a Nudel water washing method or a 70 mL precipitation method to remove soluble salts. 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.

Examples of known additives include compounds described in Research Disclosure No. 17643 (December 1978) and Research Disclosure No. 18716 (November 1979). The types of compounds shown in these two research disclosures and where they are listed are listed in the table below.

Additive RD-17643RD-1
8716 pages Classification Page Classification Chemical sensitizers 231[1648-Upper right sensitizing dye 231V648Right-649
Left development accelerator 29 III 648-Right upper blade blur prevention agent 24VI649-Right lower stabilizer 〃〃Color stain prevention agent 25 ■ 650 Left-Right image stabilizer 25
■ Ultraviolet absorber 25-26 ■ 649 right-650 left filter dye // // Brightening agent 24 V hard
Curing agent 26X651 left coating aid
Agent 26-27 n 650 right surfactant 26-27 U 650 right plasticizer 27 ■ Slip agent Static inhibitor 27 II
I // Matte agent 28
XVI 650 right binder -
26II651 left Examples of the support that can be used in the photosensitive material according to the present invention include the above-mentioned RD, 1764
3, 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 a subbing layer or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. Then, the emulsion according to the present invention can be coated on both sides of the support thus treated.

When applying the present invention to a medical X-ray guide 2 fee,
For example, a fluorescent intensifying screen whose main component is a phosphor that generates near-ultraviolet light or visible light when exposed to penetrating radiation is used. It is desirable to expose this material in close contact with both surfaces of a light-sensitive material prepared by coating both surfaces with the emulsion of the present invention.

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

Further, the fluorescent intensifying screen refers to, 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〕

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

Example 1 In this example, a silver halide photographic material was produced as follows.

First, an emulsion was prepared as follows.

(I) Preparation of monodispersed emulsion 60°C, pAg-8, pH-2,
A monodisperse cubic emulsion of silver iodobromide containing 2 mol % of silver iodide [A] was obtained. In this emulsion, the incidence of twins was 1% or less in terms of number of crystals, as seen in electron micrographs. Using this emulsion [A] as a seed crystal, it was grown as follows.

Namely, a solution containing preserved gelatin and optionally ammonia kept at 40°C8. This seed crystal [A] was dissolved in a nail, and the pH was further adjusted with acetic acid.

Using this liquid as a mother liquid, a 3.2N aqueous ammoniacal silver ion solution was added by a double jet method.

In other words, l) Ag is controlled to 7.3, l) H is controlled to 9.7,
A layer containing 30 mol % of silver iodide was formed. Next, the pH was changed from 9 to 8.2 until 95% of the particle size, and the pAg was kept at 9.0 for growth. Thereafter, a potassium bromide solution was added using a nozzle over a period of 8 minutes to reduce the pAg to 11.0, and the mixing was completed 3 minutes after the addition of potassium bromide was completed. This emulsion has an average grain size of 0.7+n and a total silver iodide content of about 2.0 mol %.

In addition, when preparing the emulsion, sensitizing dyes (1) and (2) described later were added at 300 mg and 15 mg, respectively, per mol of silver halide.
mg was added.

A desalting step was then performed to remove excess soluble salts. That is, the reaction solution was kept at 40°C, and a formaldehyde condensate of sodium naphthalene sulfonate (Japanese Patent Publication No. 35-16
Compound described in No. 086) 5 g/AgX l mol, M
g5o, 8 g/1 mole of AgX was added, stirred for 5 minutes, and then allowed to stand. After that, drain the supernatant liquid and
The liquid volume was set to 200 cc per mole. Next, 4
1 mole of 1.8α/AgX pure water at 0°C was added and stirred for 5 minutes.

Next step: 420 g of Mg/1 mol of AgX was added, stirred and left to stand in the same manner as above, and the supernatant liquid was removed to perform desalting. The solution was then stirred and postceratin was added to redisperse the AgX. The obtained emulsion is emulsion (I)
And so.

(n) Preparation of tabular grain emulsion ■D1 Ammonia water (28%) 705m
Q: B1 and 01 liquids were added in 30 seconds to A1 liquid that was vigorously stirred at 40°C by a double jet method to generate nuclei. The pBr at this time was 1.09 to 1.15.

After 1 minute and 30 seconds, CI was added for 20 seconds and aged for 5 minutes. The KBr concentration during ripening was 0.071 mol/Q, and the ammonia concentration was 0.63 mol/I2.

Thereafter, the pH was adjusted to 6.0, and desalting was performed in a conventional manner. When this seed emulsion was observed under an electron microscope, the average grain size was 0.
．． It was a monodisperse spherical emulsion with a 26 μm distribution width of 18%. Next, this was grown using the following method.

Using the above seed emulsion and the three types of solutions shown below, a silver oxide emulsion consisting mainly of tabular twins was prepared.

(1,082m by water
Maintain the QA2 solution at 75°C and disperse the aforementioned seed crystals therein.
After suspending the mixture, liquid B2 and liquid C2 were added using a double jet method. At this time, the pH was maintained at 2.0 and the pAg at 8.0 with nitric acid. The addition time was 16 minutes, and the addition rate was 1.
It was increased linearly by a factor of 27. Next, B2 liquid and B2 liquid were added to the same liquid by a double jet method. At this time, the pH was maintained at 2.0 and the pAg at 8.0.

The addition time was 38 minutes, and the addition rate was increased linearly by a factor of 1.80 between the initial and final additions. After the addition is complete, the emulsion (I
The sensitizing dye described below was added in the same manner as in ), and desalting was carried out in the same manner as described above to obtain an emulsion with a pAg of 8.5 and a pH of 5.85 at 40°C.

When the obtained emulsion was observed under an electron microscope, it was found to be 100%
Consists of twin grains, average grain size 0.95 μm, coefficient of variation υ
06.3214% silver halide emulsion, and 80% of the projected area has a grain diameter/grain thickness ratio of 2.5 to 3.
It was 0. This emulsion was designated as emulsion (II).

(In) Preparation of polydisperse emulsion The following four solutions were prepared using the forward mixing method.

Solution B and Solution C1 were poured into a reaction vessel for emulsion preparation, and stirred using a propeller type stirrer with a rotation speed of 300 revolutions/minute, and the reaction temperature was maintained at 55°C.

Next, the solution A was divided into 1 volume: 2 volumes, and 1 volume of the solution, 100 mQ, was added over 1 minute.

After continuing stirring for 10 minutes, A, the remaining 2 volumes of the liquid, 2
00 mQ was added over 10 minutes. Stirring was continued for an additional 30 minutes. Then, Solution D was added to adjust the pH of the solution in the reaction vessel to 6.0, and the reaction was stopped.

Thereafter, a sensitizing dye was added and desalted in the same manner as in Emulsion CI). The average particle size of the obtained particles was 0.56 μm, and the coefficient of variation, Ol, was 3232%. Further, the silver iodide content was 1.2 mol%.

The three types of emulsions obtained were each kept at 55°C, and ammonium thiocyanate, chloroauric acid, and hypo were added to perform gold/sulfur sensitization. After sensitization, 4-hydroxy-〇-methyl-1,3,3a, ? - Stabilized by adding tetrazaindene.

Sensitizing Dye (1) Sensitizing Dye (2) Oligomers according to the present invention as shown in Table 1 were added to the emulsions obtained as described above. In addition, as an additive, t-butyl-catechol 400+ag1 polyvinylpyrrolidone (molecular weight 10.0
00) 1.0g, styrene/maleic anhydride copolymer 2.5g, )limethylolpropane 10g, diethylene glycol 5g1, nitrophenyl-triphenylphos7onium chloride 50mg, ammonium 1.3-dihydroxybenzene-4-sulfonate 4g12
-Mercaptobenzimidazole-5-sodium sulfonate 15+ag 10 mg of 1.1-dimethylol-1-bromo-1-nitromethane was added to prepare an emulsion coating solution.

Additionally, the following compound was added as a protective layer additive. (The amount added is shown as the amount per Ig of gelatin.) CHzCOO (
CHz)*CI(s "CHCOO(CHz)zcH(CHx)z5OsNa
7m
g Matting agent made of polymethyl methacrylate with an average particle size of 7 μl 7rags Colloidal silica 70+g with an average particle size of 0.013 μl, CH2-Cl2O, CI (!0C
27 mg of 1hSO2CI (-CH) was added to prepare a coating solution for a protective layer.

Each of the obtained coating solutions was mixed with glycidyl methacrylate 5
Thickness obtained by subbing with an aqueous copolymer dispersion obtained by diluting a copolymer consisting of three monomers: 0 wt%, 10 wt% methyl acrylate, and 40 wt% butyl methacrylate to a concentration of 10 wt%. It was coated on a 180 μm polyethylene terephthalate blue haze.

That is, an emulsion layer and a protective layer were simultaneously coated on both sides of the base in order from the support, dried to obtain a sample, and then heated at 23°
The dura was left in an atmosphere of C955% RH for 3 days to stabilize the dura, and then the next development experiment was carried out.

The amount of coated silver for each sample was 4 g/m2 on both sides, and the coating liquid for the protective layer was a 3% gelatin solution, and the amount of gelatin coated on both sides, including the emulsion layer protective layer, was 6.5 g/m2. It was coated so that

The following evaluations were performed on the prepared samples.

<Measurement of sensitometry> Using the standard light B described in the "New Edition, Lighting Data Book" as the light source, use a non-filter with an exposure time of 0.1 seconds and 3.2 cm5 so that the same amount of light is applied to both sides of the film. exposed.

The processing conditions in this example are as follows. That is, the processing length of the sample photosensitive material is Q=1.9.
5 (m), and the processing time T=45C seconds).

CQ"" x T = 74.26).

The following developing solution and fixing solution were used.

(Developer) XD-5R35℃ (5RX-501, add 20mQZff equivalent of XD-5R-5 in the developer tank) (Fixer) Water 18°C (Supplied for 3, OQ 1 minute) In this example, the sample was prepared using a Konica Corporation automatic processor 5.
Treatment was performed using RX-501. The temperature at the location where the automatic processor was installed was 25° C. and the relative humidity was 62%.

For the sensitivity of each sample, calculate the reciprocal of the amount of light required to increase the blackening density by 1.0, and then calculate the sensitivity of sample No. 1 in Table 1 by 1.
It was expressed as a relative sensitivity set to 00.

<Evaluation of drying property> The processing machine and processing agent were used in the same manner as in sensitometry, and the drying property of the obtained sample was evaluated in five stages according to the following criteria.

1.Completely dry, sample 1, heat) A2,
Completely dry, the sample is cooled and strained ＼ B3, slightly damp (173 or less) C4, damp
(2/3 or less) D5, damp (2
E (Evaluation of Roller Mark Properties) Pressure resistance during development (pressure marks caused by the roller of an automatic developing machine, ie, roller marks) was evaluated as follows. That is, the sample was not exposed to light and was processed in an X-ray automatic developing machine equipped with opposed rollers and rollers of 5 Jl+.

The roller marks that occurred at that time were classified into 5 levels based on their severity and evaluated as follows.

A: No roller marks. B: Very few occurrences C: Slight occurrence (within practical tolerance) D = Frequent occurrence (outside practical tolerance) E: Very frequent occurrence (1 comparative compound H-1 number average molecular weight ? H・ CH3-C-CH.

C) lzsO=Na 163,000 As is clear from Table 1, the samples of the present invention dry faster, can be processed ultra-quickly, and have improved roller mark properties compared to the comparative samples. .

Example 2 Table 2 was prepared in the same manner as in Example 1 using emulsions I, II and ■.
Samples Nos. 13 to 21 shown in 1 were prepared. The obtained samples were processed using the same processing agent as in Example 1 using an automatic developing machine having the configuration shown in FIGS. 1 and 2 for different processing times.

The obtained results are shown in Table 2, and as is clear from the table, the samples according to the present invention have less occurrence of roller marks even when the developing model changes, and drying properties [Effects of the invention] A silver halide photographic material with high sensitivity and low roller mark generation even when rapidly processed using an automatic processor and drying quickly was obtained.

[Brief explanation of drawings]

FIGS. 1 and 2 are block diagrams of an automatic developing machine used in an embodiment of the present invention.

Claims (1)

[Scope of Claims] In a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, at least one kind selected from water-soluble oligomers is contained in the hydrophilic colloid layer. A silver halide containing 10% or more and 50% or less of the total weight of the silver halide, which is processed after imagewise exposure in a roller conveyance type automatic developing machine under the conditions represented by the following formula [A]. Photographic material. [A]l^0^. ＾7＾5×T=50～125(0.7
<l<4.0) where l represents the processing length (unit: m) when processing the photosensitive material, and T represents the time required to pass through l (unit: seconds).