JP2829675B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a halogen which has a rapid development processability, suppresses the occurrence of roller marks, and has improved drying properties. The present invention relates to a silver halide photographic light-sensitive material.

[Background of the Invention]

In recent years, the processing time of silver halide photographic light-sensitive materials has been increasing in response to user needs with an increase in film consumption, and medical light-sensitive materials are no exception.

On the maker's side, the development of the silver halide composition of the photosensitive material itself and the development accelerator are used to improve the developability, and the developer composition and processing conditions are activated to make the processing speedier. Efforts are being made.

However, one of the biggest problems that accompanies the speeding up of processing is the drying property of the photosensitive material after processing. That is, since the processing time is short, the processing is completed without being sufficiently dried, so that cracks and scratches occur.

Conventionally, various proposals have been made for such an obstacle, and as for the improvement of the drying property, as a means for reducing the water absorption of the photosensitive material, for example, as a method of increasing the degree of hardening of the gelatin film, or as a direct method For example, a technique is known in which a binder component of a silver halide emulsion layer or a backing layer, that is, gelatin is reduced to reduce water absorption.

However, these conventional techniques also have little effect on recent ultra-rapid processing.

Further, the method of reducing the weight of gelatin in a silver halide emulsion layer causes, for example, an increase in fog or a deterioration in graininess in photographic characteristics, and further, the physical resistance such as scratches tends to deteriorate. Also, it is not preferable to reduce the amount of gelatin in the backing layer. For example, it is impossible to keep the curling of the film (the phenomenon of curving toward the emulsion side or the reflection side) in a well-balanced manner. Results.

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

Therefore, the film is susceptible to a roller mark due to the roller pressure or a fluid pressure mark due to the developer, and there is a risk that these phenomena may lead to erroneous diagnosis on an image in an X-ray film.

As described above, there are many problems on the photosensitive material side in order to promote rapid processing, and a new technique for solving the problems has been strongly desired.

[Object of the invention]

Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material having a fast drying property in rapid development processing. A second object of the present invention relates to a silver halide photographic light-sensitive material which does not generate roller marks in rapid processing. Other objects will be apparent from the following description.

[Configuration of the invention]

The above objects of the present invention have been found to be achieved by the following, and have led to the present invention.

That is, in a silver halide photographic material having at least one hydrophilic colloid layer on a support, at least one selected from water-soluble oligomers having a molecular weight of 1,000 to 3,000 is used in the hydrophilic colloid layer. A silver halide photographic light-sensitive material containing from 10% to 50% of the total weight of the colloid layer, and which is processed by an automatic roller-developing machine under the conditions represented by the following formula [A] after imagewise exposure. Achieved by

[A] l ^0.75 × T = 50 to 125 (0.7 <l <4.0) where l is the processing length when processing a photosensitive material (unit:
m), and T is the time required to pass 1 (unit:
Seconds).

 Hereinafter, the present invention will be described in detail.

In the present invention, the water-soluble oligomer is not necessarily required to have high solubility in water, but refers to one having solubility in water.

For example, about 0.05 g or more may be dissolved in 100 g of water at 20 ° C., preferably 0.1 g or more. The water-soluble oligomer used is preferably as high as possible in a developing solution or a fixing solution, and the solubility thereof is preferably 0.05 or more, more preferably 100 g of the developing solution.
It is preferable to dissolve 0.5 g or more, and particularly preferable to dissolve 1 g or more.

In the present invention, the oligomer is a low molecular weight polymer having a degree of polymerization of about 10 to 14 and a molecular weight of up to about 20.000.

By including the water-soluble oligomer according to the present invention in a hydrophilic colloid layer of a silver halide photographic light-sensitive material, it is possible to obtain sufficient drying property in a short time due to a small amount of water retention as compared with gelatin and rapid processing. Becomes possible. It has more surprisingly been found that the roller mark resistance by the automatic processor is also improved.

The water-soluble oligomer may be natural or synthetic.

Among the water-soluble oligomers that can be used in the present invention, examples of the synthetic water-soluble oligomer include those having a nonionic group in the molecular structure, those having an anionic group, and those having both a nonionic group and an anionic group. Can be mentioned. 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, and a phosphoric acid group or a salt thereof.

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 the natural water-soluble oligomer include those having a nonionic group, those having an anionic group, and those having both a nonionic group and an anionic group in the molecular structure.

As a preferred water-soluble oligomer, the following general formula [I]
And especially those containing 10 to 100 mol% of this in one molecule of the polymer.

These synthetic water-soluble oligomers are known compounds, for example, West German Patent Application (OLS) No. 2,312,708, US Pat.
620,751, 3,879,205, JP-B-43-7561 and the like, or a method analogous thereto.

In the formula, R ¹ and R ² may be the same or different and each is 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, a propyl Group, butyl group, etc., and those having a substituent), a halogen atom, or —CH ₂ C
Represents OOM ¹ .

L is -CONH-, -NHCO-, -COO-, -OCO-, -CO
-Or -O-.

J represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms (including those having a substituent; for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group, a hexylene group, and the like; ), An arylene group (including those having a substituent, such as a phenylene group and the like with a substituent attached thereto), an aralkylene group (including those having a substituent).
For example Or CH ₂ CH ₂ O _m CH _{2 n} , (M represents an integer of 0 to 40, and n represents an integer of 0 to 4).

Q is a hydrogen atom or Or R ³ , wherein M ¹ and M ² represent a hydrogen atom or a cation group, and R ⁹ is an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group or the like or Represents a substituent), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and
R ⁸ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a hexadecyl group or the like or a substituent thereof), alkenyl Group (for example, a vinyl group, an aryl group, or the like or a substituent thereof), a phenyl group (for example, a phenyl group, a methoxyphenyl group, a chlorophenyl group, or the like or a substituent thereof), or an aralkyl group (for example, a benzyl group). X represents an anion, and p and q each represent 0 or 1.

Y represents a hydrogen atom or _L p J _{q Q.}

When L is other than -CONH- and -NHCO-, the synthetic water-soluble monomer constituting the unit represented by the general formula [I] can be copolymerized with an ethylenically unsaturated monomer. Examples of the copolymerizable ethylenically unsaturated monomer include styrene, alkylstyrene, and hydroxyalkylstyrene (where the alkyl group has 1 to 4 carbon atoms such as methyl,
Preferred are ethyl, butyl, etc.), vinylbenzenesulfonic acid and salts thereof, α-methylstyrene, 4-vinylpyridine, N-vinylpyrrolidone, monoethylenically unsaturated esters of aliphatic acids (for example, vinyl acetate, vinyl propionate and the like) ), Ethylenically unsaturated monocarboxylic or dicarboxylic acids and salts thereof (eg, acrylic acid, methacrylic acid), maleic anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (eg, n-butyl acrylate, N , N-diethylaminoethyl methacrylate, N, N-diethylaminomethyl methacrylate).

Next, specific compounds of the synthetic water-soluble oligomer having a repeating unit represented by the general formula [I] are exemplified, but the present invention is not limited thereto.

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

When using the above-mentioned synthetic water-soluble oligomer, those having a molecular weight of 1,000 to 3,000 are preferably used.

Next, examples of the natural water-soluble polymer that can be used in the present invention include those described in detail in a comprehensive technical data collection of a water-soluble polymer water-dispersible resin (publishing department of Business Development Center). In particular, lignin, starch, burlan, cellulose, alginic acid, dextran, dextrin, guar gum, gum arabic, pectin, casein, agar, xanthan zam, cyclodextrin, locust bean gum, tragacanth gum, carrageenan, glycogen, laminaran, lichenin, nigellan, And their derivatives.

Derivatives of natural water-soluble oligomers include sulfonation, carboxylation, phosphorylation, sulfoalkylation,
Alternatively, carboxyalkylated, alkyl phosphorylated, and salts thereof, polyoxyalkylene (eg, ethylene, glycerin, propylene, etc.), and alkylation (methyl, ethyl, benzyl, etc.) are preferable.

Among natural water-soluble oligomers, glycose polymers,
And derivatives thereof are preferred, and among the glycose polymers, and derivatives thereof, starch, glycogen, cellulose,
Likenin, dextran, nigeran and the like are preferred, and dextran and its derivatives are particularly preferred.

Dextran is a polymer of α-1,6-linked D-glycose and is generally obtained by culturing dextran-producing bacteria in the presence of saccharides. Thus, the separated dextran sucrose can be obtained by reacting with saccharides. Further, these native dextrans are reduced to a desired molecular weight by a partial decomposition polymerization method using an acid or an alkaline enzyme, and the intrinsic viscosity is reduced to 0.03.
A range of ~ 2.5 can be obtained.

The dextran-modified product includes dextran sulfate, carboxyalkyl dextran, and hydroxyalkyl dextran.

The molecular weight of these natural water-soluble oligomers is 1,000-3.0
Use the one for 00.

Methods for producing these dextrans and derivatives thereof are described in JP-B-35-11989, U.S. Patent 3,762,924, JP-B-45-12820, JP-B-45-18418, JP-A-45-40149, and JP-A-46-40.
No. 31192.

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

The hydrophilic colloid layer referred to in the present invention means a layer adjacent to an emulsion layer such as a light-sensitive or substantially light-sensitive 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 light-sensitive material according to the present invention can be subjected to development processing by a commonly used known method.

The developer may be a commonly used developer such as hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-
Those containing a single substance such as p-aminophenol or p-phenylenediamine or a combination of two or more thereof are used, and conventional additives can be used.

A developer containing an aldehyde hardener can also be used in the silver halide light-sensitive material according to the present invention, for example, maleic dialdehyde such as dialdehydes, glutaraldehyde and sodium bisulfite thereof. A well-known developer in the field of photography containing

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

L, which is the processing length when processing the light-sensitive material of the present invention,
The range is more than 0.7 and less than 4.0 (unit: m). l is 0.7
In the following cases, each processing step may be reduced and the sensitivity may be reduced. Further, when the present invention is applied to an apparatus for transporting a photosensitive material by a roller type, the number of rollers to be used is reduced and transportability is deteriorated. On the other hand, if l is 4.0 or more, the transport speed becomes too high, and the film tends to be scratched.

The product of l ^0.75 and T is 50 or more and 125 or less. If this value is less than 50, the sensitivity of the photosensitive material is reduced,
Alternatively, color retention can be a problem. More preferably l
That is, the product of ^0.75 and T is 76 or more.

On the other hand, if the product of l ^0.75 and T exceeds 125, the graininess of the photographic image deteriorates even though the sensitivity hardly increases,
Fog also increases.

When processing using an automatic developing machine, it is preferable to use a roller-conveying automatic developing machine, in which case the number of all conveying rollers, the value obtained by dividing the processing length l by the number of rollers is in the range of 0.01 to 0.04. Is preferable. The time of each processing part is preferably in the following range.

Inserting + developing + migratory 25-40% Fixing + migratory 12-25% Washing + migratory 10-25% squeeze + drying 25-45% total 100% The roller used is 12mm-60mm
The length is preferably between 30 cm and 110 cm, and various materials can be used. For example, bakelite-based materials (which may include glass powder, metal powder, and plastic powder) in the areas of development, fixing, washing, and drying are used. And rubber (neoprene, isoprene, silicone rubber, etc.). It is preferable to use water-repellent and elastic silicon rubber or the like, or "Kurarino" (trade name, a product of Kuraray Co., Ltd.), a synthetic leather having high water absorption, for the transition portion and the squeeze portion.

Processing solutions such as a developing solution and a fixing solution used for processing are
An appropriate material can be used depending on the photosensitive material.

1 and 2 denote the first roller at the photosensitive material insertion port, 2 denotes the last roller at the drying outlet, 3a denotes the developing tank, 36 denotes the fixing tank, 3c denotes the washing tank, and 4 denotes the processing tank. 5, a squeezing section, 6 a drying section, and 7 a dry 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, but particularly high sensitivity is obtained. From the viewpoint, silver iodobromide is preferred.

The silver halide grains in the photographic emulsion are cubic, octahedral,
All crystals grown isotropically, such as tetradecahedrons, polyhedral crystals such as spheres, twins with plane defects, or mixtures or composites thereof Is also good. The size of these silver halide grains may be as large as 0.1 μm or less to 20 μm.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, in Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23, Emulsion Preparation and Types and (RD) No. 18716 (November 1979), page 648. It can be prepared by the method described.

The emulsion of the silver halide photographic light-sensitive material according to the present invention is described in, for example, "The theory of the photographic material" by TH James.
Process, 4th edition, published by Macmillan (1977), pp. 38-104, GFDauffin, "Photographic Emulsion Chemistry", "Photogr
aphic emulsion Chemistry ", published by Focal press (1966
), P. Glafkides, "Physics and Chemistry of Photography", Chimie et p.
hysique photographique "published by Paul Montel (1967),
VLZelikman et al., "Manufacture and coating of photographic emulsions", "Making a
nd coating photographic emulsion "prepared by the method described in Focal press (1964).

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

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

Examples of the silver halide emulsion preferably used in the present invention include, for example, JP-A-59-177535, JP-A-61-802237, and JP-A-61-802237.
And the internal high iodine type monodispersed particles disclosed in JP-A-132943, JP-A-63-49751 and Japanese Patent Application No. 63-238225. The crystal wall of the crystal may be cubic, tetradecahedral, octahedral, and a mixture of (1,1,1) and (1,0,0) planes between them.

The monodisperse emulsion referred to here means at least the number or weight of particles by a conventional method, for example, when the average particle diameter is measured.
95% of the particles are within ± 40% of the average particle size, preferably ±
The silver halide grains are within 30%. The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The crystal structure of the silver halide may be different from the silver halide composition inside and outside.

The emulsion according to a preferred embodiment of the present invention is a core / shell type monodisperse emulsion having a clear two-layer structure comprising a low iodine shell layer in a high iodine core portion.

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

Methods for producing such monodispersed emulsions are known, for example, J. Pho
t.Sic.12.242 to 251 (1963), JP-A-48-36890,
Nos. 52-16364, 55-142329, 58-49938, British Patent 1,413,748, U.S. Patents 3,574,628, and 3,655,394.

As the above-mentioned monodisperse emulsion, an emulsion in which grains are grown by using a seed crystal and supplying silver ions and halide ions using the seed crystal as a growth nucleus is particularly preferable. still,
Methods for obtaining core / shell emulsions are described, for example, in British Patent
No. 1,027,146, U.S. Pat.Nos. 3,505,068, 4,444,877,
This is described in detail in Japanese Patent Application Laid-Open No. Sho 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, for example, improvement in spectral sensitization efficiency, improvement in graininess and sharpness of images, and the like, for example, UK Patent 2,112,157, US Patent 4,439,520,
4,433,048, 4,414,310, 4,434,226, JP-A-58-113927, 58-127921, 63-138342,
It can be prepared by the methods described in JP-A Nos. 63-234272 and 63-305343.

The above-mentioned emulsions are either emulsions of a surface latent image type in which a latent image is formed on the grain surface, an internal latent image type in which a latent image is formed inside the grain, and a type in which a latent image is formed on the surface and inside. Is also good.
These emulsions may use a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a Nudel washing method or a flocculation sedimentation method to remove soluble salts. As a preferred washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or JP-A-63-15 / 1988
As a particularly preferred desalting method, a method using G3, G8, etc., as an example of an aggregated polymer agent described in No. 8644 can be mentioned.

In the emulsion according to the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure No. 17643 (December 1978) and No. 18716 (1919).
November 1979). The following table shows the types and locations of the compounds shown in these two research disclosures.

Examples of the support that can be used in the light-sensitive material according to the present invention include, for example, page 28 of RD.17643 and page 64 of RD.18716.
Those described in the left column on page 7 can be mentioned.

A suitable support is a plastic film, etc.
Generally, the surface of these supports may be provided with an undercoat 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 the present invention is applied to medical X-ray radiography, for example, a fluorescent intensifying screen mainly containing a phosphor that generates near-ultraviolet light or visible light by exposure to penetrating radiation is used. It is desirable that this is brought into close contact with both surfaces of a light-sensitive material obtained by coating the emulsion of the present invention on both surfaces and then exposed.

The penetrating radiation referred to here is a high-energy electromagnetic wave and means X-rays and gamma rays.

The fluorescent intensifying screen is, for example, an intensifying screen mainly containing calcium tungstate as a fluorescent component, or a fluorescent intensifying screen mainly containing a rare earth compound activated with terbium.

EXAMPLES Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

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

 First, an emulsion was prepared as follows.

(I) Preparation of Monodisperse Emulsion Monodisperse cubic silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm by a double jet method while controlling at 60 ° C., pAg = 8 and pH = 2.0. Emulsion (A) was obtained. From the electron micrograph of this emulsion, the incidence of twinning was 1% or less in number. This emulsion (A) was grown as a seed crystal as follows.

That is, the seed crystal (A) was dissolved in a solution 8.5 containing, if necessary, a gelatin preserved at 40 ° C. and ammonia, and the pH was adjusted with acetic acid.

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

That is, the pAg was controlled at 7.3 and pH 9.7, and the silver iodide content was 30.
A mol% layer was formed. Next, adjust the pH to 9 to 95% of the particle size.
From 8.2 to 8.2, with pAg of 9.0. Thereafter, a potassium bromide solution was added by a nozzle over 8 minutes, and pAg was added to 11.
The mixture was dropped to 0, and the mixing was completed 3 minutes after the addition of the potassium bromide. This emulsion had an average grain size of 0.7 m and the silver iodide content of the whole grain was about 2.0 mol%.

In preparing the emulsion, sensitizing dyes (1) and (2)
Was added in an amount of 300 mg and 15 mg, respectively, per mol of silver halide.

Next, a desalting step was performed to remove excess soluble salts. That is, the reaction solution was kept at 40 ° C., and 5 g / AgX1 mol of formaldehyde condensate of sodium naphthalenesulfonate (compound described in JP-B No. 35-16086) and 8 g of MgSO ₄ 8 g / AgX1 mol were added. did. Thereafter, the supernatant was discharged to a liquid volume of 200 cc per mole of AgX. next,
1 mol of pure water at 40 ° C. was added at 1.8 / AgX, and the mixture was stirred for 5 minutes.
Then MgSO ₄ 20g / AgX 1 mol was added and stirring allowed to stand in the same manner as described above, to eliminate the supernatant was desalted. The solution was then stirred and post-gelatin was added to re-disperse AgX. The resulting emulsion was designated as emulsion (I).

(II) Preparation of tabular grain emulsion II The A ₁ solution was stirred vigorously at 40 ° C., was added B ₁ and C ₁ solution by a double jet method at 30 seconds, it was carried out the production of nuclei. The pBr at this time was 1.09 to 1.15.

After 1 minute 30 seconds, was added in 5 minutes aging C ₁ in 20 seconds. During ripening, the KBr concentration was 0.071 mol / and the ammonia concentration was 0.63 mol /.

Thereafter, the pH was adjusted to 6.0, and desalting was performed by a usual method. When this seed emulsion was observed with an electron microscope, the average particle size was 0.
This was a monodisperse spherical emulsion having a size of 26 μm and a distribution width of 18%.
Next, this was grown by the following method.

Using the above seed emulsion and the following three solutions, a silver halide emulsion mainly comprising tabular twins was prepared.

Keeping the A ₂ solution 75 ° C., it dispersion of seed crystals described above, was suspended, it was added B ₂ solution and C ₂ solution by a double jet method. At this time, the pH was maintained at 2.0 with nitric acid and the pAg at 8.0. Addition time is 16
The addition rate was linearly increased so that the initial and final addition rates were 1.27 times. Next, Solution D _{2 and} Solution E ₂ were added to the same solution by a double jet method. At this time, the pH was kept at 2.0 and the pAg was kept at 8.0. The addition time was 38 minutes, and the addition rate was increased linearly so as to be 1.80 times at the beginning and at the end. After completion of the addition, the sensitizing dye described below was added in the same manner as in Emulsion (I), and desalting was performed in the same manner.
Thus, an emulsion having a pAg of 8.5 and a pH of 5.85 was obtained.

When the obtained emulsion was observed with an electron microscope, it was 100%
Consists of twin grains, average grain size 0.95μm, coefficient of variation
^{06.32 A} 14% silver halide emulsion with a projected area of 80%
% Was a particle diameter / particle thickness ratio of 2.5 to 3.0. This emulsion was designated as emulsion (II).

(III) Probably preparation of acid emulsion The following four kinds of solutions were prepared by a forward mixing method.

Solution B _{3 and} solution C ₃ were poured into a reaction vessel for emulsion preparation, and the number of rotations was 30.
Stir with a propeller-type stirrer at 0 revolutions / min.
C.

Then A ₃ solution 1 volume: 2 split the percentage of volume, was charged with 100ml of 1 volume of them over a period of 1 minute. Stirring was continued for 10 minutes and poured over 200ml of 2 volumes of residual A ₃ solution for 10 minutes. Stirring was continued for another 30 minutes. Then, the addition of D ₃ solution, the solution pH in the reaction kettle was adjusted to 6.0, the reaction was stopped.

Thereafter, a sensitizing dye was added in the same manner as in the emulsion (I), and desalting was performed. The average particle size of the obtained particles was 0.56 μm, and the coefficient of variation was ^υ06.32, 32%. The silver iodide content was 1.2% by mole.

The obtained three kinds of emulsions were each kept at 55 ° C., and ammonium and thiocyanate, chloroauric acid and hypo were added thereto to perform gold / sulfur sensitization. After completion of the sensitization, the mixture was stabilized by adding 4-hydroxy-6-methyl-1,3,3a and 7-tetrazaindene.

To the emulsions obtained as described above, the oligomer according to the present invention was added as shown in Table 1. As an additive, t-butyl-catechol 400 per mole of AgX was used.
mg, polyvinylpyrrolidone (molecular weight 10,000) 1.0 g, styrene / maleic anhydride copolymer 2.5 g, trimethylolpropane 10 g, diethylene glycol 5 g, nitrophenyl-triphenylphosphonium chloride 50 mg, 1,3
-Ammonium dihydroxybenzene-4-sulfonate
4g, 2-mercaptobenzimidazole-5-sulfonic acid 1,1-dimethylol-1-bromo1-nitromethane 10 mg
Was added to obtain an emulsion coating solution.

The following compounds were added as additives for the protective layer.
(The amount of addition is shown per 1 g of gelatin.) 7 mg of matting agent composed of polymethyl methacrylate having an average particle diameter of 7 μm, and colloidal silica 70 having an average particle diameter of 0.013 μm
mg, CH ₂ = CHSO ₂ CH ₂ OCH ₂ SO ₂ CH = CH ₂ 7 mg was added to prepare a coating solution for a protective layer.

Glycidyl methacrylate
Thickness obtained by diluting a copolymer consisting of three types of monomers of 50 wt%, methyl acrylate 10 wt%, and butyl methacrylate 40 wt% so that the concentration becomes 10 wt%, and using an aqueous dispersion of the copolymer to obtain a thickness. It was coated on a 180 μm polyethylene terephthalate blue base.

That is, two layers of an emulsion layer and a protective layer were simultaneously coated in order from the support on both sides of the base and dried to obtain a sample.
The film was allowed to stand for 3 days in an atmosphere of 55 ° C. and 55% RH to stabilize the hardened film, and then the next development experiment was performed.

The silver coating amount of each sample was 4 g / m ^{2 on} both sides, and the coating solution for the protective layer was a 3% gelatin solution, and the coated gelatin amount including the protective layer on the emulsion layer was 6.5 g / m ² on both sides. It was applied so that

 The following evaluation was performed about the created sample.

<Measurement of Sensitometry> Using standard light B described in "New Edition, Illumination Data Book" as a light source, both sides of the film were exposed with a non-filter at an exposure time of 0.1 second and 3.2 cms so as to have the same light amount.

The processing conditions in the present embodiment are as follows.
That is, the photosensitive material as a sample has a processing length l = 1.95.
In (m), the processing time T was set to 45 (seconds). (L ^0.75 × T
= 74.26).

 The following developer and fixer were used.

(Developer) XD-SR 35 ℃ (SRX-501, XD-SR-S in the developing tank
(Fixing solution) XF-SR 33 ° C, 63cc / replenish with 1 sheet (washing water) Tap water 18 ° C (supplied at 3.0 / min) In this example, the sample was automatically developed by Konica Corporation. Machine
Processing was performed using SRX-501. The temperature at the place where the automatic developing machine was installed was 25 ° C., and the relative humidity was 62%.

The sensitivity of each sample was obtained by calculating the reciprocal of the amount of light required for increasing the blackening density by 1.0, and expressing the relative sensitivity with the sensitivity of sample No. 1 in Table 1 being 100.

<Evaluation of drying property> The processing machine and the processing agent are processed in the same manner as in sensitometry.
The drying property of the obtained sample was evaluated in five steps according to the following criteria.

Dryness evaluation criteria 1. Completely dry, sample is warm A 2. Completely dry, sample is cold B 3. Slightly wet (less than 1/3) C 4. Wet (2 / 5 or less) D 5. Wet (exceeds 2/3) E <Evaluation of roller mark property> The pressure resistance during development (pressure mark by roller of automatic developing machine, that is, roller mark) is as follows. evaluated. That is, without exposing the sample, the sample was processed by an X-ray automatic developing machine having a special roller having a strong concavo-convex having a facing roller.

The roller mark generated at that time is 5
The classification was made into stages and the evaluation was made as follows.

A: No roller mark is generated. B: Slightly generated. C: Slightly generated (within practical tolerance) D: Frequently generated (outside practical tolerance) E: Extremely large

As is clear from Table 1, the sample of the present invention has a faster drying property, can be processed very quickly, and has improved roller mark properties as compared with the comparative sample.

Example 2 In the same manner as in Example 1, Table 2 was prepared using emulsions I, II and III.
Sample Nos. 13 to 21 shown in FIG. The obtained samples were processed with the same processing agents as in Example 1 using an automatic developing machine having the structure shown in FIGS. 1 and 2 to change the processing time.

The obtained results are shown in Table 2. As is clear from the table, the samples according to the present invention were less likely to generate roller marks even when the developing model was changed, and were excellent in drying property.

[Effects of the Invention] According to the present invention, a high-sensitivity silver halide photographic light-sensitive material can be obtained in which the generation of roller marks is small and the drying property is high even when the processing is carried out quickly by an automatic developing machine.

[Brief description of the drawings]

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

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/04 G03D 3/00

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein said hydrophilic colloid layer contains at least one water-soluble oligomer having a molecular weight of 1,000 to 3,000. Containing 10% or more and 50% or less of the total weight of the hydrophilic colloid, and being processed after imagewise exposure by a roller transport type automatic developing machine under the condition represented by the following formula [A]. Silver halide photographic light-sensitive material. [A] l ^0.75 × T = 50-125 (0.7 <l <4.0) where l is the processing length (unit: m) when processing the photosensitive material
Represents the time required to pass 1 (unit: seconds)
Represents