JPH0218543A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance productivity and to decrease film fogging in an ultra-rapid processing by confining the time from coating of an emulsion on a base contg. silver halide particles from which the dissolved matter is removed by a specific treatment to the end of drying within 3 minutes. CONSTITUTION:The dissolved matter of the silver halide particle is flocculated, settled and removed by an amino group-substd. flocculating gelatin agent is which >=50% of the amino acid group of gelatin particles is substd. with an acyl group or carbamoyl group, etc., and is converted to modified gelatin. the silver halide emulsion contg. such silver particles is coated on a base and is dried. The time before the end of drying to 4-12% moisture content when the moisture content of the film attains equil. at 23 deg.C and 55% is confined within 3 minutes.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic material, and particularly to a silver halide photographic material which is highly productive and has improved fog.

[Background of the invention]

In recent years, the consumption of silver halide photographic light-sensitive materials has continued to increase, and as a result, the number of sheets of silver halide photographic light-sensitive materials processed has increased significantly.

For this reason, there is a demand for further speeding up the development process of silver halide photographic materials, that is, increasing the throughput within a certain period of time.

This trend is also seen in the field of X-ray sensitive materials, such as medical X-ray films. In other words, the number of medical examinations is increasing due to the enforcement of regular health examinations, and the number of examination items is increasing in order to make the diagnosis more accurate, resulting in a remarkable increase in the number of X-ray photographs taken.

It is also necessary to notify the patient of the diagnosis result as quickly as possible.

For this reason, there is a strong demand for rapid processing and use for diagnosis. In particular, for angiography photography, intraoperative photography, etc., it is necessary to be able to view the photographs as quickly as possible.

Furthermore, recently, especially as the number of medical X-ray examinations has increased, the total amount of irradiated x-rays has inevitably increased, so there is a strong demand for reducing the exposure dose during examinations.

For this reason, it is desired to develop a photographic material that can produce precise images with a small amount of X-rays, that is, a photographic material with a higher frequency range.

From this point of view, for example, Japanese Patent Application Laid-Open No. 62-223752
No. 62-267739, JP-A-62-267739, JP-A-62-267739
As described in Japanese Patent No. 286037, high sensitivity and ultra-rapid processing (for example, total processing time of 20 to 6
0 seconds) has been proposed.

On the other hand, in the manufacturing process of photographic materials that can be processed extremely quickly, technological developments are being made to reduce costs and improve productivity by increasing the coating speed.

In order to increase the coating speed, the emulsion layer is usually
A common method is to reduce the drying load by making the film thinner, thereby rapidly shortening the drying time.

However, when such a method is adopted, the fog of the film becomes high in most cases, making it difficult to make an accurate diagnosis, for example, in the case of an X-ray photograph that is directly interpreted using the film.

[Purpose of the invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material that is highly productive and exhibits low film fog even when subjected to ultra-rapid processing.

[Structure of the invention]

The above-mentioned object of the present invention is obtained in a silver halide photographic light-sensitive material having at least a silver halide emulsion layer provided on a support, by condensation and sedimentation using an amine group-substituted agglomerated gelatin agent to remove dissolved substances. This is achieved by a silver halide photographic material in which a silver halide emulsion containing silver halide grains is coated on a support and dried, and the time from coating to completion of drying is within 3 minutes.

In this silver halide photographic material, it is desirable that the time from coating the silver halide emulsion onto the support to completion of drying is 90 seconds or more and 3 minutes or less.

By the way, the total coating film thickness of silver halide emulsion etc. is 40 to 7
0 μm is preferable, and the time from application to completion of drying is within 3 minutes, but the film thickness in the drying process is 12 to 30 μm.
When drying, the dry bulb temperature is 25.0 to 35.0°C, and the difference between the dry bulb temperature and wet bulb temperature is 4 to 12°C. Ball temperature is 28
．． It is dried using drying air having a temperature of 0 to 38.0°C and a difference between dry bulb temperature and wet bulb temperature of 3 to 11°C.

In addition, the completion of drying as referred to in the present invention means that the moisture content of the film reaches equilibrium at 23°C and 155%, and the moisture content is 4 to 12%.
state.

Moreover, the coating film thickness here refers to the film I! on which the coating liquid is applied to the support. , and is calculated using the following formula. Coating may be done in any number of layers at the same time, and refers to the total film thickness of those coated at the same time.

Any means may be used to apply the silver halide emulsion or other liquid to the support, and examples include dip coating, roller coating, curtain coating, extrusion coating, and the like. For more information, see Research Disclosure Volume 176, pages 27-28.
ng Procedures J.

The temperature during coating is preferably 25 to 45°C, and the coating speed is preferably 30 to 200 m/7 minutes.

In the silver halide photographic light-sensitive material of the present invention, the amino group-substituted agglomerated gelatin agent accounts for 50% of the amino groups in the gelatin molecule.
Modified gelatin with the above substitutions is desirable.

Examples of substituents for amine groups in gelatin are given in U.S. Pat.
．． As described in No. 691.582, No. 2,614,928, and No. 2.525.753, substituents useful in the present invention include (1) alkylacyl, arylacyl, Acyl groups such as acetyl and substituted or unsubstituted hendiyl; (2) carbamoyl groups such as alkylcarbamoyl and arylcarbamoyl; (3) sulfonyl groups such as alkylsulfonyl and arylsulfonyl; (4) alkylthiocarbamoyl and arylthiocarbamoyl; thiocarbamoyl group, (5) straight chain or branched alkyl group having 1 to 18 carbon atoms, (
6) Substituted or unsubstituted aryl groups such as aromatic heterocycles such as phenyl, naphthyl, pyridyl, and furyl.

Among these, preferred modified gelatin has anlu group (-
COR') or carbamoyl method (-CON(R')R2
).

Note that R' is a substituted or unsubstituted aliphatic group (e.g., an alkyl group having 1 to 18 carbon atoms, an allyl group), an allyl group, or an aralkyl group (e.g., a phenethyl group), and R2 is a hydrogen atom or an aliphatic group. , an aryl group, and an aralkyl group.

Particularly preferred is the case where R1 is an aryl group and R2 is a hydrogen atom.

Specific examples of amine group-substituted agglomerated gelatin agents are illustrated below using amino group substituents, but the present invention is not limited thereto.

, Exemplary agglomerated gelatin agent (amino group substitution): CH.

Co-C-CH3 0CHi CH3 CON It CH3 The amount of these amino-substituted flocculated gelatin agents used for desalting is 0.3 to 10 times the amount of gelatin contained as a protective gelatin during desalting ( (weight) is suitable, and particularly preferably about 1 to 5 times the amount (weight).

Note that the desalting treatment of silver halide grains using the amino group-substituted agglomerated gelatin agent, that is, the removal of soluble salts, may be carried out during the preparation of seed crystals, during growth, or after the completion of growth (after physical ripening). .

Next, grains used in the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention will be described.

The particle size distribution of the particles used may be monodisperse. Here, monodisperse means a dispersion system in which 95% of the particles fall within ±60%, preferably within 40%, of the number average particle size. Further, the number average grain size is the number average diameter of the projected area diameter of silver halide grains.

Alternatively, the emulsion may be made of an emulsion in which ultratabular silver halide grains having a grain diameter of 5 times or more the grain thickness occupy 50% or more of the total projected area. For details, see JP-A-58-12
It is described in Publication No. 7921, Publication No. 5B-113927, etc.

It is preferable that at least 80% of the silver halide grains contained in the photosensitive silver halide emulsion layer in the present invention have a regular structure or shape in terms of weight or number of silver halide grains.

Here, the term "silver halide grains with a regular structure or morphology" means grains that grow isotropically without including anisotropic growth such as twin planes, such as cubic, tetradecahedral, regular octahedral, It has a shape such as a facepiece or a sphere. The method for producing such regular silver halide grains is described, for example, in the Journal of
Photographic Science (J, Photo, Sc
i, ), 5.332 (1961), Ber, Bunsen
ges, Phys, Chem,) 67, 949 (
1963), International, Combres of
Photographic Science of Tokyo (
Intern, Congress Photo, Sci
, Tokyo (1967)).

In the production of monodisperse emulsions and/or emulsions with regular halogenated grains, Japanese Patent Publication No. 4B-3689
Publication No. 0, Publication No. 52-16364, JP-A-5514
The method described in Japanese Patent No. 2329 can be preferably used.

In the practice of the present invention, the silver halide grains used in the light-sensitive silver halide emulsion layer are, for example, TH, James
Author: The Theory of the Photographic Process
t.

graphic Process), 4th edition, l'lB
c; Mlllan Publishing (1977), P, Glfk
ides, Chimie et Physique Photo
ographique (Paul Monte1, 1967), G. F. Duffin, Photographic Ink Emulsion Chemistry I. Lii, (Photo
ograpl+ic [imulsionChemis
try) (The Focal Press, 196
6 years), V, L.

Making and Coating Photographic Emulsions by Zelikmanetal
Kingand Coating Photograp
hic Emulsion), (The Focal P
It can be manufactured by applying the method described in the literature such as (Res., 1964).

When forming silver halide grains, ammonia, for example, is used as a silver halide solvent to control grain growth.
Rhodankali, Rhodanammon, thioether compounds (e.g. U.S. Patent Box 3,271.157, U.S. Pat. No. 3,574)
, No. 628, No. 3,704,130, No. 4.29
7.439, 4,276.374, etc.), thione compounds (e.g., JP-A-53-144319, JP-A-53-144319, JP-A-53-144319, JP-A-53-144319)
No. 82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.), etc. can be used. Among them, ammonia is preferred.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In addition, these silver halide grains or silver halide emulsions contain iridium, thallium, palladium, rhodium,
It is preferable that at least one salt (soluble salt) of zinc, nickel, cobalt, uranium, thorium, strontium, tungsten, and platinum is contained. Its content is preferably between 1o-6 and 1o per mol PAg.
-1 mole.

Particularly preferably, at least one of thallium, palladium, and iridium salts is contained. These may be used alone or in combination, and the addition position (time) is arbitrary. This improves flash exposure characteristics,
Prevention of pressure desensitization, prevention of latent image progression, sensitization and other effects are expected.

In practicing the present invention, at least during particle growth prior to chemical sensitization as described above, the pAg of the mother liquor containing protective colloid is
An embodiment in which the is 10.5 or more can be preferably adopted. Particularly preferably, an atmosphere with a very high bromine ion excess of 11.5 or more is passed through at least once.

In this way, the number of (111) planes can be increased and the particles can be rounded. The (111) plane of such particles preferably accounts for 5% or more of the total surface area.

In this case, the increase rate of the (111) plane (the increase rate with respect to that before passing through the above pAg atmosphere of 10.5 or more)
is preferably 10% or more, more preferably 10 to 20%.

The outer surface of the silver halide grain is the (111) plane or the (10
0) How to measure whether one side is covered or the ratio thereof is reported by Akira Hirata,
Bulletin of the Society of Scientific Photography of Japan No. 1
3.5-15 (1963).

In this case, the timing to set the above pHg is approximately 2 of the total amount of added silver.
It is preferable to do this after the addition of 73 is completed and before the desalting step. This is because it is easy to obtain a monodispersed emulsion with a narrow particle size distribution.

In addition, aging in an atmosphere where pAg is 1095 or more is 2
It is preferable to do this for at least 1 minute.

A preferred embodiment of the present invention is a silver halide photographic emulsion layer in which the photosensitive silver halide emulsion layer consists essentially of silver iodobromide and contains silver halide grains having a multilayer structure, the silver halide emulsion layer containing silver halide grains having a multilayer structure. The difference in the average iodine content of any two adjacent layers (between the coating layers or between the inner core and the coating layer) each having a homogeneous iodine distribution of the particle is 10 mol% or more, and the average iodide content of the outermost layer is 10 mol% or more. There is an embodiment in which the silver content is 10 mol % or less and the silver halide grains are a chemically sensitized halide emulsion layer.

Here, a particle having a multilayer structure is one in which a coating layer consisting of an arbitrary halogen composition is provided on the outside of the inner core, and this coating layer may be only one layer, or may have two or more layers, for example, three layers.
A layer or four layers may be stacked. Preferably the number of layers is 5 or less.

As the silver halide for the inner core and the coating layer, silver bromide, silver iodobromide, and silver iodide are used, but a mixture with a small amount of silver chloride may be used.

Specifically, silver chloride may be contained in an amount of about 10 mol% or less, preferably about 5 mol% or less.

Further, the outermost layer is substantially silver bromide or substantially silver iodobromide (iodine content: 10 mol % or less), and may contain less than several mol % of chlorine atoms.

For example, in x-green light-sensitive materials, silver iodide may increase problems such as inhibition of development and infectious development, so it is practically preferable to keep the content of silver iodide below a certain level.

The silver iodide content is preferably 10 mol% or less in the entire grain,
It is more preferably 7 mol% or less, and most preferably 0.1 to 3 mol%.

When the inner core is made of silver iodobromide, it is preferably a homogeneous solid solution phase. Here, being homogeneous can be more specifically explained as follows.

That is, when performing X-ray diffraction analysis of silver halide grain powder, the surface index of silver iodobromide [2
00] means that the half width Δ2θ of the peak is 0.03 (deg) or less. The conditions for using the diffractometer at this time are to set the scanning speed of the goniometer to ω(d
eg/m1n), ω7/r when the time constant is γ (sec) and the receiving slit is r (mm).
≦10.

As for the halogen composition of the internal core, the average iodine content is preferably 40 mol% or less, more preferably 0 to 40% by mole.
It is 20 mol%.

The difference in silver iodide content between two adjacent layers (any two coating layers or coating layer and inner core) is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably is 25 mol% or more.

In addition, the silver iodide content of the coating layer other than the surface coating layer is as follows:
Preferably it is 10 to 100 mol%.

When silver halide grains consist of three or more layers and the coating layer is made of silver iodobromide, it is not necessary that they all be homogeneous, but all layers must be made of homogeneous silver iodobromide. is preferred.

In the case of a negative-working halide daughter emulsion, such a coating layer (or inner core) having a high silver iodide content is preferably present below the outermost surface. In the case of a positive silver halide emulsion layer, it may be present either inside or on the surface.

The silver iodide content of the outermost coating layer is preferably 10 mol% or less, more preferably 0 to 5 mol%.

Here, regarding the silver iodide content of the inner core of the silver halide grains and the coating layer used in the photosensitive silver halide emulsion layer of the present invention, for example, J.
dstein), D. B., Wil.
lams) 'X-ray analysis in TEM/ATEM
Scanning Electron Microscope (1
977), Volume 1 (I IT Research Institute), Page 651 (March 1977).

When the silver halide grains in the photosensitive silver halide emulsion layer of the present invention are composed of two layers, for example, it is preferable that the inner core has a higher iodine content than the outermost layer, and when it has three layers, the inner core preferably has a higher iodine content than the outermost layer. It is preferable that the coating layer other than the surface layer or the inner core has a higher iodine content than the outermost layer.

The silver halide grains in the photosensitive silver halide emulsion layer of the present invention may be of positive type or negative type.

For chemical sensitization, for example H, Fr1eser lla
Die-Grundlagen der Fotografissien Prozesse Mituto Zilbel Halogennieden (
Die Grundlagen der Photog
raphischenprozesse mit Si
lberhalogeniden), Akadeimish Verlagesellschaft (^kademisch)
eVeragase11schaft) 1968, 6
The method described on pages 75-734 can be used.

Further, a spectral sensitizing dye may be added at any time from the time of silver halide grain formation to the time of chemical ripening or coating.

The spectral sensitizing dye is preferably added from the time when 60 to 100% of the final volume of silver halide grains is formed until the end of chemical ripening.

Specific examples of spectral sensitizing dyes include, for example, page graphide (
"Chimie Photographigue" by P. Glafkides
” (2nd edition, 1957: Poemlemontre Paris (P
aul Montel Paris)) Chapters 35-4
Chapter 1 and Hay7 (P.M., Hamer), “The Cyanine and Related Combinations”
Cyanine ar+dReiated Compo
unds) J (Interac
ience)), and U.S. Patent No. 2,503,776
No. 3,459.553, No. 3,177.21
No. 0, Research Discology +- (Research
Disclosure) Volume 176 19643 (197
(Issued in December 2008) Section 23 (■), Section 1, etc.

Sensitizing dyes may be used alone or in combination.

When a sensitizing dye is used in the present invention, it can be used at the same concentration as used in a normal negative-working silver halide emulsion. In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion. Approximately 1.0 x 10-5 to 5. O
Xl0-' mole, especially about 4.0 Xl0-5 to 2.0 sensitizing dye per mole of silver halide. It is preferred to use a concentration of OXl0-' molar.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (
For example, U.S. Patent Nos. 2,933.390 and 3,63
5,721), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like.

Preferred spectral sensitizing dyes include the following.

The photographic emulsion used in the light-sensitive silver halide emulsion layer of the present invention contains various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. can be done.

For more information, see Stabilization by E. J. Birr.
Of Photographic Silver Halide Emulsions (Stabilization of T'h
otographic Silver Halide E
mulsions), Focal Press, 1
Please refer to 974 etc.

As the binder or protective colloid that can be used in the hydrophilic colloid layers such as the emulsion layer, intermediate layer, and protective layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids may also be used. It can be used alone or together with gelatin.

Examples of hydrophilic colloids include gelatin derivatives, graft polymers of gelatin and other polymers, albumin,
Proteins such as casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, There are a wide variety of synthetic hydrophilic polymeric materials such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylpyrazole, polyvinylpyrazole, and the like.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer.

The photographic light-sensitive material of the present invention may contain a dispersion of a water-insoluble or poorly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability or the like.

The silver halide photographic material of the present invention is preferably provided with a protective layer, and this protective layer is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one described above. Note that the protective layer may be a single layer or a multilayer.

A matting agent and/or a smoothing agent may preferably be added to the emulsion layer or protective layer of the silver halide photographic light-sensitive material of the present invention.

Various other additives may be used in the photographic material of the present invention, if necessary. Examples include dyes, development accelerators, optical brighteners, color antifoggants, and ultraviolet absorbers. Specifically, Research Discology'r-(Re
Search Disclosure), Volume 176,
Those described on pages 22 to 31 (RD-17643, 1978) can be used.

The silver halide photographic material of the present invention may also be provided with an antihalation layer, intermediate II, filter layer, etc., if necessary.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers can be embodied by being coated on one or both sides of a flexible support commonly used in photographic light-sensitive materials. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. For more information,
Research Disclosure + - (ResearchD
isclosure), Vol. 176, p. 25.
Those described in the section pports J are used.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclo +
(RD-1764) No. 176, pp. 25-30
Any of the various methods and various treatment liquids described in 3) can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. The processing temperature is usually 18
The temperature may be lower than 18°C or above 50°C.

Further, various other developing methods (for example, thermal development, etc.) may be used depending on the case.

〔Example〕

Examples of the present invention will be described in detail below.

It should be noted that, as a matter of course, the present invention is not limited to the examples described below.

Example 1 In this example, a 180 μm polyester support was subjected to corona discharge treatment, and a 48:50:2 (weight ratio) copolymer latex of butadiene/styrene/acrylic acid (40% x) was applied to the support. 100cc and distilled water 890cc
and 10 cc of a 10-t% solution of 2,4-dichloro-6-hydroxy-5-triazine sodium salt was applied at a rate of 7 cc/m2, Dry for a minute. Note that this subbing layer treatment was performed on both sides of the support.

An emulsion and a protective layer solution prepared as shown below were coated onto the support on which the subbing layer was formed as described above.

Preparation of A8 seed crystals Monodispersed cubic silver iodobromide containing 42% silver iodide 2mo with an average grain size of 0.3 μm was prepared by the double jet method at 60°C, pAg=8, and pH=2.0. Crystal particles were prepared.

Then, the reaction solution containing the obtained particles was divided into three parts, and each part was desalted by the method shown below to obtain three types of seeds (T-1, T-2, and T-3).

Desalting method of T-1 Add a condensate of sodium naphthalene sulfonate and formalin (compound shown below) to the reaction mixture after mixing at 40°C. Exemplary compound ¥11J) and MgSO4 each at 15g/AgX 1mol,
After adding 60 g/1 mole of AgX and stirring for 3 minutes, the mixture was allowed to stand and the peelable salt was removed by decantation to obtain T1.

Desalting method of T-2 - Add compound (1) to the reaction solution after mixing at 40°C (amino group-substituted agglomerated gelatin agent of C-8 described above, degree of substitution 90).
%) was added, and after stirring for 3 minutes, KO)10.
Add 13 g/8 g x 1 mol, set p)l to 4.0, let stand, and decant. After that, add 40゛C pure water 2.1 1/^g
Add 0.25 g/8 g x 1 mole and stir for 5 minutes at pH 5.8.

Then) INO: l (1,7N) 1.5CC/8gX
1 mole was added to give p) 14.3, and the peelable salt was removed by standing and decantation to obtain T-2.

Desalting method of T-3 Perform the same operation except that compound (1) (amino group-substituted agglomerated gelatin agent of G-5 described above, degree of substitution 90%) is used instead of compound H in the desalting method of T-2. Conduct, T-3
I got it.

Growth from B1 seed crystals Particles were grown in the following manner using the above-mentioned seed crystals of T-1, T-2, and T-3.

First, seed crystal T-1 was dissolved in a solution 8.51 containing protected gelatin and optionally ammonia kept at 40°C, and the pH was further adjusted with acetic acid.

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

In this case, ρ11 and EAg were changed as needed depending on the silver iodide content and crystal habit.

The emulsion contained monodisperse grains with a total silver iodide content of about 2 mo 1% and an average grain size of 0.53 .mu.m.

Next, this reaction solution was divided into three parts, and excess soluble salts were removed by desalting methods (1), (2), and (3) as shown below.

Desalination method a.

1. Add 5.5 g/Ag
/AgX 1 mol was added, stirred for 3 minutes, and left to stand still.
Perform decantation.

After adding and dispersing 1.8j2/AgX 1-E of pure water at 2.40°C, 50420 g of Mg/1 mole of AgX was added, and after stirring for 3 minutes, the mixture was allowed to stand still and decanted.

Repeat step 3.2 again.

4. Add gX1 mole and water to 15g/after gelatin, 45
After finishing to 0 cc/1 mol of AgX, stir at 55°C for 20 minutes to disperse.

In this way, emulsion I-1 was obtained.

Desalting method Inlet 1: Add 50 g/Ag
110 cc of IAc/1 mol of AgX was added to lower the pif to 5.0, and the mixture was allowed to stand and decanted.

2. After adding 1.8β/AgX 1 mol of pure water at 40°C, add KO86.8g/AgX 1 mol, and make pif 6.
．． 0 and disperse.

After being well dispersed, 70 cc of 56-t% llAc/
Add 1 mole of AgX to adjust the pH to 4.5, let stand, and decant.

Repeat step 3.2 again.

4. After that, add 15g/^gX1 mol of post-gelatin and KOI
I Add 1 mol of Ig/AgX and water, 450cc/Ag
Finish to 1 mole of X.

In this way, emulsion 1-2 was obtained.

In addition, in the same manner, particles were grown using seed crystal T-2,
Emulsion 1-3 was prepared by the desalting method described in A.
Emulsion 1-4 was obtained by growing grains using Emulsion 1-2 and using the desalting method described above.

In the desalination method, compound ■ is substituted for compound ■ in the desalination method port.
Emulsions ① to 5 were obtained by performing the same procedure except for using .

Further, when emulsion 1-5 was obtained, seed crystal T-3 was used instead of seed crystal T-2 to obtain emulsion 1-6.

Preparation of monodisperse particles without using C8 seed crystals. Preparation method similar to seed crystals, i.e. 60° CT: pAg8,
A halogen salt aqueous solution and a silver salt aqueous solution were added to pl+2.0 by a controlled dotafluent method to obtain grains with an average silver iodide content of 2 mo 42% and an average grain size of 0.53 μm.

This emulsion was desalted in the same manner as for T-1 to T-3 to obtain emulsions 1-7, I-8, and I-9.

These particles I-1 to I-9 were each treated with ammonium thiocyanate at a concentration of 1.9 Xl0- per mole of silver.
3 moles, and appropriate amounts of chloroauric acid and hypo and the above-mentioned spectral sensitizing dyes (a) and (a)) in a weight ratio of 200:1 in a total amount of soomg per mole of silver halide. Chemical ripening is carried out, 15 minutes before the end, potassium iodide is added at 200 mg per mole of silver, then stabilized with 3xio-2 moles of 4-hydroxy-6-methyl-1,3,3a7-titrazaindene, and the additions described below. and lime-treated gelatin, and for each of emulsions 1-1 to [-9, the finished amount per mole of silver halide was changed in two ways depending on the amount of water added, and emulsions 1-1a, 1-1b, and 1-2 were prepared.
a.

I-2b, I-9a and I-9b were prepared in the same manner.

All emulsions were made to have a density of 13 cp at 35°C by adjusting the amount of thickener (copolymer of styrene and maleic acid).

The total amount of gelatin contained in the emulsion per mole of silver halide was 130 g.

The finishing amount per mole of silver halide for each emulsion is as follows.

l-1a=1-9a Finished amount per mole of each silver halide 2774 ml-1b-1-9b
Finished amount per 111 moles of each Halodef
3205nI! .

The additives used in the emulsion solution (silver halide coating solution) are as follows. The amount added is expressed per mole of silver halide.

1.1-dimethylol-1-bromo-1 nitromethane
70 mg Sodium 2-mercaptobenzimidazole-5 sulfonate 1.5 mg H The protective layer solution was prepared as follows. The amount added is expressed per 11 coating liquids.

Lime-processed inert gelatin 6E1g acid-processed gelatin 2g t-butyl-catechol 400mg polyvinylpyrrolidone (molecular weight 10,000) 1.0g styrene-maleic anhydride copolymer 1-4g trimethylolpropane
10g diethylene glycol
5g nitrophenyl-triphenylphosphonium chloride 50mg ammonium 13-hydroxybenzene-4-sulfonate
4g polymethyl methacrylate (matting agent with area average particle size 3.5μm)
1.1g silicon dioxide particles (area average particle size 1.2μm
(matting agent) 0.5
g-dox AM (colloidal silica manufactured by DuPont) 3
0g 2% aqueous solution of 2-4-dichloro-6-hydroxy 1.3.5-)riazine sodium salt (hardener) Formalin 35% (hardener) Glyoxal aqueous solution 40% (hardener) 10 mj2 mj2 The protective layer has an amount of gelatin of 1 to give 1.5 mE CH2C0O(CHz)qcH3 1.75 g/m2.
．． 22g/m2, and similarly l-1
The emulsion solution and protective layer solution of b to 1-9b were heated on two machines so that the emulsion layer had a silver content of 1.75 g/m2 and the protective layer had a gelatin content of 1.02 g/m2 per side. Both sides were coated simultaneously using a slide hopper coater.

Table 1 shows the coating film thickness of each emulsion in combination with the protective layer.

Table 1 C1□HzsCONH (ClhCHzO→-, -11F
+qCq O−iC1l□CH2O±rc Cl□C
H,-OH Sodium chloride 1.1g 0mg 3mg The l-1a-1-9a emulsion solution and protective layer solution prepared as above were each coated on one side with a silver content and under the drying conditions described below. Let it dry, Document No. 1-No.
I got 66.

From the end of drying to just before winding up each sample, the conditions were 32°C and 60% relative humidity, and during winding, the conditions were 25°C and 57% relative humidity.

All samples were tested at a temperature of 5°C for 25 seconds immediately after application.
Electric heating coefficient of wind with relative humidity of 80% is 30 (Kcal/m2
hr°c).
After that, the dry bulb temperature was 30°C until the film thickness reached 30μm.
? For 35 seconds with dry air at a W bulb temperature of 15°C,
Drying was performed by varying the amount of drying blast.

Until the film thickness reaches 30 to 12 μm, the dry bulb temperature is 32°C.
1 Dry air with a wet bulb temperature of 24°C for 60 seconds to reduce the film thickness to 12μ
The drying air volume was adjusted so that drying was performed in 45 seconds from m to the end of drying (moisture content of 30% or less).

Furthermore, by changing the coating speed as shown in Table 2, the time from coating to drying was varied.

The relationship between the coating speed and the time until the end of drying is determined by the coating speed (m
/min] x time until completion of drying [minutes] = 165 m].

The obtained sample was heated at 25 °C and 36 °C under 55% relative humidity.
After that, the following processing agents (developing solution and fixing solution) were put into an automatic developing machine 5RX-501 (manufactured by Konica Corporation), and processing from development to drying was performed in 45 seconds.

The dry film thickness of each sample was 3.6 μm.

[Developer]

Potassium sulfite 70gHydroxyethylethylenediaminetriacetic acid Trilium acetate
8g 14-dihydroxyhensen 28g boric acid
10g5-methylbenzotriazole 0.04
g1-phenyl-5-methylcaptotetrazole 0.0
1g sodium metabisulfite 5g acetic acid (9
0%) 13g Triethylene glycol 15g 1-phenyl-3-hyrazolidone 1.2g 5-nitroindazole 0.28 Glutaraldehyde 4.0g Ethylenediaminetetraacetic acid 2
Sodium 2.0g Potassium Bromide
4.0g 5-nitrohenshiimidazole
1. Make an aqueous solution of Og1P and adjust the pH to 10 with potassium hydroxide.
, 50 liquids.

(Fixer) Sodium diosulfate pentahydrate 45g Disodium ethylenediaminetetraacetate 0.5g Ammonium thiosulfate 150g Anhydrous sodium sulfite 8g Potassium acetate
16g Aluminum sulfate 10-18 hydrate 27
g Sulfuric acid (50-%) 6g
citric acid 1g nitric acid
7g glacial acetic acid
Glacial acetic acid was added to make 5g11 of an aqueous solution to give a pH of 4.0.

The washing water of an automatic developing machine runs at 1.51 m/min at a temperature of 18°C.
Shared.

The fog density of the processed and developed sample was measured using a densitometer PDA-65 (manufactured by Konica Corporation). The density of the support was measured in advance, and the fog value obtained by subtracting the density of the support from the density of (fog+support) is listed in Table 2.

Table 2 shows that for the samples according to the present invention, low fog samples were obtained even after drying for a short time of less than 170 seconds.

Example 2 Preparation of emulsion Preparation of tabular grains (aspect ratio 5-30) 10.5 g of MBr, 1,000 olether (HO (CHz)) in water IJ2
zS(Cut)ts(C}It) zs(Ctlz)
Q}l) 10 cc of 0.5 i+t% aqueous solution and 30 g of gelatin were added and dissolved, and maintained at 70°C.

Into this solution, while stirring, 0.88 mol/IV. of silver nitrate aqueous solution 30mIV. and 0.88mon/1
of potassium iodide and potassium bromide (molar ratio 3.5:96.
30 ml2 of the aqueous solution of 5) was added by double jet method.

After the addition of the mixture was completed, the temperature was lowered to 40°C. then 3
One is the compound I and the other is MgSO. 24.6 g/Ag
Emulsion II-1 was prepared by adding 1 mole of X.

Also, the remaining two are the above-mentioned escape method ports. , c. Desalting was carried out to obtain emulsions If-2 and II-3.

These emulsions n-1 to II-3 were chemically ripened in exactly the same manner as in Example 1, and the emulsions prepared in the same manner as f-1a were U-1a, II-2a, If-3a. ,I
n-1b, n-2 adjusted in the same way as -1b
b, +1-3b.

Emulsions U-1a to II-3a, I1 prepared as above
-1b to II-3b and the protective layer solution prepared in Example 1 were applied and dried using the same drying device. At this time U-1a
~ II-3a is similar to 1-1a, the total coating thickness is 60μ,
For II-1b to II-3b, the amount of coating liquid supplied was adjusted so that the total coating thickness was 70 μm, similar to I-1b.

Furthermore, as shown in Table 3, the coating speed was varied and the time from coating to drying was varied.

From Table 3, it can be seen that for the samples according to the present invention, low fog samples were obtained even after drying for a short time of 3 minutes or less.

Table 3 sample emulsion total coating Drying completed mosquito No. No. Film thickness speed For up to Bu [μ import [IIll minutes] time [seconds] Li U-1a 0,04 outside invention No 〃 0.05 l no II 0.05 No 〃 0.07 No No 0.09 〃 〃 0. IC If-1b 0.05 〃 Nono 0.05 No 〃 0.05 〃 〃 0.08 No No 0.08 No No 0.09 If-2a 0.05 present invention 〃 No 0.0! : No l no 0.05 n-2b 0.04 1st floor 〃 〃

Claims (1)

[Claims] A silver halide photographic material having at least one silver halide emulsion layer on a support, containing silver halide grains obtained by condensation and sedimentation with an amino group-substituted agglomerated gelatin agent to remove dissolved substances. 1. A silver halide photographic material comprising a silver halide emulsion coated on a support and dried, the time from coating to completion of drying being within 3 minutes.