JP2683737B2 - Silver halide photographic light-sensitive material excellent in ultra-rapid processability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]   The present invention is a silver halide photographic light-sensitive material having excellent ultra-rapid processability.
About the material. The invention is not in the field of X-ray films, for example.
Available at [Conventional technology]   In recent years, the consumption of silver halide photographic light-sensitive materials has increased.
It's going on. For this reason silver halide photographic light-sensitive materials
The number of processed materials increases, which speeds up the development process.
It is required to increase the processing amount in the same time.
You.   The above tendency is due to the fact that X-ray sensitive materials such as medical X-ray filters
In the field of programs. In other words, enforce regular medical examinations
As the number of diagnoses increases rapidly due to factors such as
The number of inspection items has increased, and X-ray photographs have been taken.
The number is increasing, while the diagnostic results
It is also necessary to inform the recipient. Therefore such medical treatment
To meet the demands of the world, automation of diagnosis (such as shooting and
Etc., and process X-ray film more quickly.
There is a need to.   Development process (development, fixing, washing, drying
One way to shorten the time is to increase the transport speed.
is there. However, it is processed with a roller transport type automatic processor.
If you are trying to reduce the processing time,
-If the transfer speed is increased, (a) the concentration will not be sufficient.
Degree, contrast, decrease in maximum density), and (b) fixing
(C) Insufficient water washing of the film
And (d) the film is not sufficiently dried.
Occurrence and insufficient fixing and insufficient washing with water are being stored in the filter
The change in color tone causes deterioration of image quality.   One way to solve these problems is to increase the amount of gelatin.
It is to reduce, but for a film with a small amount of gelatin,
Graininess of photographic images is likely to deteriorate. Also, between films
If it is rubbed or if the film is rubbed with another substance
In the case of the so-called abrasion, the density after development is higher than other areas.
Blackening also easily occurs.   Although ultra-rapid processing is desired as described above,
The ultra-rapid processing referred to in this specification means that the film is processed by an automatic processor.
After inserting the tip of the developer tank, transfer section, fixing tank, transfer
Film passing through parts, washing tank, split parts, and dry parts
The entire time until the tip of the
If the total length (m) of the processing line is
c.) divided by (sec.)] is more than 20 seconds and less than 60 seconds
Say processing. Why you should include the transit time here
As is well known to those skilled in the art,
The liquid from the previous process swelled in the gelatin film even during
Since it is moisturized, it can be considered that the treatment process is in progress.
To do so.   Japanese Patent Publication No. 51-47045 discloses a method for rapid processing.
Although there is a description of the importance of the amount of ratin, even with this technology
The processing time is 60 seconds to 120 seconds including the transitional part.
Therefore, it is not possible to meet the recent demand for ultra-rapid processing.
I can't.   On the other hand, photographic materials have higher sensitivity.
Has been requested. For example, in the case of X-ray sensitive materials,
Recently, due to the increase in medical X-ray examination, not only the medical world but also the international
As public opinion, there is a strong demand for reduction of radiation dose.
Because of this, photographic materials that can obtain precise images with a small X-ray dose,
In other words, the development of photographic materials with higher sensitivity is desired.   How to increase sensitivity with the same grain size
There are various technologies. Use the appropriate sensitization technique
The same grain size, that is, the covering power is maintained.
It is expected that the sensitivity can be increased while holding it. This technique
As a technique, for example, a development accelerator such as thioethers
Addition to emulsion, spectrally sensitized silver halide
For emulsions, a method of supersensitizing a combination of appropriate dyes, or
There are many reports of improved technology for optical sensitizers,
These methods are not necessarily high-sensitivity silver halide photographic light-sensitive materials.
It is hard to say that it is versatile in terms of fees. That is, high sensitivity
For silver halide emulsions for silver halide photographic light-sensitive materials,
The above method tends to cause fog during storage.   Furthermore, in the field of medical X-ray photography, it has been
Ortho-sensitized from regular type with long range
, Ortho-type photosensitivity in the wavelength range of 540 to 550 nm
Materials are being used. Such sensitization
The photosensitive material has a wide photosensitive wavelength range and high sensitivity.
Therefore, X-ray dose can be reduced and
The impact on it can be reduced. In this way, dye sensitization is extremely high
Is a useful sensitizing method, but there are still many unsolved problems.
Sufficient sensitivity depending on the type of photographic emulsion used.
There are problems such as not being able to do so. [Object of the invention]   The object of the present invention is, for example, in the case of high-speed processing as described above.
Such as ultra-quick processing with a total processing time of 20 seconds or more and less than 60 seconds
The above-mentioned problems of the prior art can be solved even when
And excellent in sensitivity, fog, graininess, etc.
To provide a photographic light-sensitive material. [Configuration of the invention]   The object of the present invention is to provide the support on at least one side of the support.
Two or more types of surface latent image type halogens with qualitatively different photographic characteristics
Having a photosensitive silver halide emulsion layer containing a silver halide emulsion,
At least one unit of the two or more types of silver halide emulsions
And a light-sensitive silver halide emulsion layer.
A photosensitive silver halide emulsion layer to which a sensitizing dye has been added
The amount of gelatin on the side having a hydrophilic colloid layer containing 2.00
~ 3.50g / m^TwoSilver halide photographic feeling characterized by
Achieved by optical material.   Here, the monodispersity is the following coefficient of variation regarding the particle size.
It means that VC is 0.20 or less. However, S is the standard deviation,Given by Is the average particle size, ri is the i-th particle
The diameter and ni are the number of particles.   The light-sensitive material of the present invention has at least one of its supports.
Side, halogenation of two or more types with substantially different photographic characteristics
Contains a silver emulsion. One emulsion layer has two or more types of
It may contain a silver rogenide emulsion or a certain emulsion layer
By containing different emulsions from other emulsion layers
The above two or more emulsions should be contained on one side of the support.
It may be   In the light-sensitive material of the present invention, a light-sensitive silver halide emulsion is used.
At least one agent layer is provided on one side of the support.
Or at least one layer on each side of the support
It may be done.   The light-sensitive material of the present invention contains a light-sensitive halogenated compound if necessary.
It is possible to have a hydrophilic colloid layer in addition to the silver emulsion layer.
For example, a protective layer is preferably provided. The feeling of the present invention
The optical material is a hydrophilic roller containing a photosensitive silver halide emulsion layer.
The amount of gelatin on the side with the id layer is 2.00 to 3.50 g / m^TwoRange of
Surrounded by Photosensitive emulsion layer only on one side of support
If so, the amount of gelatin on that side must be within the above range.
However, if a photosensitive emulsion layer is present on both sides of the support, both
It is necessary that the amount of gelatin on each side be within the above range. Feeling
When there is no hydrophilic colloid layer other than the light-sensitive emulsion layer,
The amount of gelatin in the photosensitive emulsion layer must be within the above range.
You.   Thus, the light-sensitive material of the present invention has a photosensitive layer on a support.
The hydrophilic colloid layer on the side having the silver halide emulsion layer (halo
(Including the silver genide emulsion layer) has a gelatin content of 2.00 to 3.50
g / m^TwoIt is. In this range, the amount of gelatin is 2.00 g / m^Two
3.50 g / m, less coating failure than less^TwoThan
The drying property is better than when the amount is large. And the amount of gelatin
Is more preferably 2.40 to 3.40 g / m^TwoAnd 2.50-3.30g /
m^TwoIs more preferable. By taking such an aspect
The degree and the like can be further improved.   Hereinafter, the present invention will be described in more detail.   The light-sensitive material of the present invention comprises two or more kinds having substantially different photographic characteristics.
It contains the above silver halide emulsion, but here "substantially
"Different photographic characteristics" means sensitivity, gradation, color sensitivity, and coloration.
Of photographic characteristics including image quality, developability, image sharpness, graininess, etc.
Of these, at least the sensitivity and gradation should be different.
You.   In a preferred embodiment of the present invention, it is used in the present invention.
There are two types of silver halide emulsions with different photographic characteristics.
It is preferably 6 or more and 6 or less.   At least one kind of silver halide emulsion is a monodisperse emulsion.
However, a polydisperse emulsion may be used in combination. In that case, any
In terms of ratio, both monodisperse and polydisperse can be used.
Good. Particularly preferred in the present invention is two or more types of milk.
In this embodiment, all the agents are monodisperse emulsions.   In addition, in the present specification, the monodispersity is a variation related to the particle size.
It means that the coefficient is 0.20 or less. That is, the standard deviation S is The coefficient of variation VC is given by Given by Therefore, the monodispersity of the emulsion in this specification
Is defined by S / ≦ 0.20. In addition, when simply saying monodispersity
, It means that it is substantially monodisperse.   Also, polydispersity means, for example, by The Photo
Graphic Journal (The Photographic Journa
l),79, 330-338 (1939) by Trivelli and Smith
When measuring the average particle size by the reported method, the number of particles
Or at least 10% of the particles by weight deviate from the average particle size by 40%.
It refers to the state of particle size distribution in which the particles have been distributed.   The particle size as used herein refers to spherical silver halide grains.
Is its diameter, and in the case of particles with a shape other than spherical,
Is the diameter of a sphere of equal volume.   Determine the particle size with a centrifugal separation type Stokes diameter measuring instrument
And can be measured with an electron micrograph.   Emulsion silver halide set used in the practice of this invention.
The composition is arbitrary for each emulsion and each emulsion.
The respective compositions may be the same. Of similar composition
You may use. In addition, to achieve the required characteristics
Can be arbitrarily selected.   Examples of silver halides that can be used in the practice of the present invention include
For example, silver chloride, silver bromide, silver iodobromide, silver chlorobromide and mixtures thereof.
There is a compound. Particularly, silver iodobromide is preferably used. Smell
When silver iodide is used, the content of silver iodide is not particularly limited.
However, it is preferably 0.2 mol% to 10 mol%. this
In this case, silver iodide is preferably concentrated inside.   When silver iodide is included as a mixed crystal, its distribution is arbitrary.
However, it is desirable that silver iodide is concentrated inside.   The grain size of silver halide grains is not particularly limited
However, those having an average particle size of 0.1 to 3 μ are preferable. More preferred
It is preferably 0.3 to 2 μ.   In addition, these silver halide grains have improved flash exposure characteristics.
Salt for sensitivity, sensitivity, logic for gamma regulation
Photographic features such as um salts or thallium salts for improving pressure resistance
Even if various metal salts for sex adjustment are doped
Good.   In carrying out the present invention, a monodisperse emulsion was used as the emulsion.
When preparing the monodisperse emulsion, a halogen
Water-soluble silver salts and water-soluble halogens accompanying the growth of silver halide grains
It is desirable to increase the addition rate of the compound. Addition speed
By making the particle size distribution more monodisperse,
Mixing time is shortened, which is advantageous for industrial production. Also halo
Reduces the chance of structural defects being formed inside the silver gentide grains
It is also preferable in that And how to speed up this addition
For example, Japanese Patent Publication Nos. 48-36890 and 52-16364, JP-A-55
-142329, the silver salt aqueous solution and the halo
Continuous or stepwise addition of genide solution
You may increase. The upper limit of the above addition rate is new nuclear particles
A flow velocity just before the occurrence of
g, degree of stirring, composition of silver halide grains, solubility, grain
Depending on the diameter, distance between particles, type and concentration of protective colloid, etc.
Therefore, it changes.   A method for producing a monodisperse emulsion is known, for example, J. Phot. Sel. 1
2,242 ~ 251 (1963), Japanese Patent Publication No. 48-36890, No. 52-16364
And JP-A-55-142329.
Adopting the technology described in Japanese Patent Laid-Open No. 57-179835
You can also.   The silver halide emulsion used in the present invention is a core / shell.
Type monodisperse emulsion may be used.
The agents are known from JP-A-54-48521 and the like.   A polydisperse emulsion is used as an emulsion in the practice of the present invention.
In this case, a known method may be used for producing the polydisperse emulsion.
it can. For example, “The Theory of the Photo” by T.H. James
graphic Process "4th edition, published by Macmillan (1977) 38-
Neutral method, acidic method, Ann
Monia method, forward mixing, double jet method, controlled
・ Double jet method, conversion method, core / shear
It can be manufactured by applying a method such as the Ru method.   As another example of the polydisperse emulsion, the grain size is 5 of the grain thickness.
Halogen composed of tabular silver halide grains that is more than double
Examples thereof include silver halide emulsions.   Such tabular silver halide grains can be prepared by methods known in the art.
Can be prepared.   For example, Hidemaru Sakai, Ph.D.
As described in "Research on Manufacturing Method of Silver Paper"
Precipitation on small tabular grains prepared with pBr under similar conditions
It is known how to grow by adding ungrown fine particles
Have been.   Further, as described in JP-A-58-113928,
Initially substantially free of iodide ions, pBr 0.6-1.6
After preparation, grow by adding silver salt, bromide, iodide
Method, and as described in JP-A-58-127921, pBr
40% or more by weight of tabular grains in an atmosphere of 1.3 or less
Forming seed crystals that maintain the same pBr value
Method of growing seed crystals while simultaneously adding a rogen solution
It has been known.   In the practice of the present invention, each emulsion is
Suitable chemical sensitization can be performed.   When chemical sensitization is performed, for example, sodium thiosulfate,
Sulfur sensitization method using thiourea compounds, chloroaurate, three
Gold sensitization method using gold chloride, thiourea dioxide, salt first
Reduction sensitization using tin, silver aging, etc., other palladium sensitization
Sensing method, selenium sensitizing method, etc. are used by themselves.
In addition, two or more of them can be used in combination.   In this case, it is particularly preferable to use gold sensitization and sulfur sensitization together.
preferable.   Further, reduction sensitization can be performed inside the grains.   In the practice of this invention silver halide grains are halogenated.
Some silver halide emulsions contain iridium, thallium and palladium.
Mu, rhodium, zinc, nickel, cobalt, uranium, g
Salts of Li, Strontium, Tungsten and Platinum
Of the (soluble salts), at least one is contained
preferable. Its content is preferably 10 per mole Ag.
^-1~Ten^-6Is a mole. Particularly preferred is thallium or para.
Contains at least one of the salts of dium and iridium
Is to be done. These can be used alone or mixed
The addition position (time) of the addition is arbitrary. This makes the flash
Improve exposure characteristics, prevent pressure desensitization, prevent latent image fading,
Feeling and other effects are expected.   The grain shape in the silver halide emulsion is arbitrary. An example
For example, cubic, tetradecahedron, octahedron, hexahedron, twin, round
Things, so-called potato-shaped, flat-shaped, etc.
Can also be used. Also, treatment with potassium bromide or solvent
Particles can also be used.   As a preferred embodiment of the present invention, it is used as described above.
In some cases, all emulsions are monodisperse emulsions.
If three types of monodisperse emulsions are used, the characteristic curve
It has a relative maximum sensitivity as an emulsion for the legs.
Responsible for the average particle size of 0.4 to 3 μm and the direct part
An average grain size of 0.4-
About 1.5 μm, as the emulsion responsible for the maximum density part
The average particle size of 0.2 to 0.8 μm with relative minimum sensitivity is used.
Preferably. Another preferred embodiment of the present invention
As described above, at least one polydisperse emulsion is contained as described above.
However, in this case, the polydisperse emulsion is used in combination with the milk.
It has the highest sensitivity among the agents and the average particle shape is 0.4 to 3 μm.
Are preferred.   Internal latent image type halogenation described in JP-B-41-2086
Combined use of silver particles and surface latent image type silver halide particles
You can also.   The silver halide photographic light-sensitive material of the present invention has a small number of supports.
At least one silver halide emulsion layer on at least one side
Therefore, even in a multi-layer structure, a single-layer structure
Is also good. If it is a single layer, two or more kinds of emulsions should be included in this layer.
Will be included. In a multi-layered structure, one of the two is 2
May contain more than one emulsion, or all layers
Since more than one type of emulsion will be coated as a whole,
Is also good.   It is also possible to mix two or more emulsions as appropriate,
It is also possible to form multiple layers and apply each layer separately.   The emulsion layer can be formed on both sides of the support. So
If two or more emulsions are coated on both sides,
It may be only one side. For both sides, two or more types of milk
The agents may be in the same combination or in different sets.
You may take a combination.   The light-sensitive material of the present invention is suitable for ultra-rapid processing,
For example, in a preferred embodiment, the total processing time is 20 seconds or less.
Should be processed by an automatic processor that is less than the top 60
Is mentioned.   The silver halide photographic light-sensitive material of the present invention can be used, for example, as a roller.
When processing with a conveyor type automatic processor, in most cases, development processing ~
Processed in the dry state, but dryness and other properties
The water content of the photographic light-sensitive material is 6.0 in order to obtain good performance.
~ 15.0g / m^TwoThe range is preferably 9.0 to 14.
0g / m^TwoIs preferred. Halogenation in this specification
The water content of a silver photographic light-sensitive material is defined as the temperature at 25 ° C and relative humidity of 75%.
Under the circumstances, it means the one obtained by the following measuring method. That is, 20
Give as much exposure as required to obtain maximum density, cm x 20 cm.
The obtained sample is automatically processed by Konishi Rokusha Kogyo Co., Ltd. KX-50
0 (at processing speed changeover switch 90 seconds) is used.
The outline is shown in Fig. 1), and the developing solution is Konishi Roku Photo Industry Co., Ltd.
Specified starter XD-90S (manufactured by the same company) for Sakura XD-90
Amount was used, and this was used at 35 ° C, and the fixer was
Sakura New XF (manufactured by the same company) is used at 32 ℃, and the washing water is 18 ℃
Of tap water is supplied at 3 minutes per minute for automatic development.
went. Drying rack of automatic processor (indicated by reference numeral 92 in FIG. 1)
(Shown) is removed, and the same sample as the water content measurement sample is removed.
101 sheets are continuously processed at intervals of 1 sheet / 12 seconds, and the 101st sample
Was used as the water content measurement sample, and the squeeze rack (marked in Fig. 1
(Shown in No. 91), pull out at the exit, and wait for 15 seconds
Measure the quantity. (At this time, the power of the dry system is not turned on.
Modify in advance. )   The weight at this time is W_w(G).   Next, after the sample is sufficiently dried, it is kept at 25 ° C 55 ° C for 1 hour or more.
Let stand under the condition of% RH and measure its weight. W this_d
(G). The water content is calculated from the following formula. Water content (g / m^Two) = W_w-W_d× (10000 cm^Two/ 20cm × 20cm)   In addition, the weight measurement place must be a place where the wind speed is 0.5 m / sec or less.
I have to.   The light-sensitive material of the present invention has a melting time of 8 minutes.
It is preferable to be set to 45 minutes. The amount of gelatin is within the range of the present invention.
And the melting time within this range
By this, the above-mentioned preferable water content range can be achieved.   The melting time is more preferably in the range of 12 minutes to 40 minutes.
It is to be surrounded, and most preferably 15 to 30 minutes
That is.   Melting time is, for example, 1 cm x 2 cm.
Material without stirring in 1.5% caustic soda solution kept at 50 ℃
The time until the emulsion layer elutes can be measured.
You can find out by   Use a hardener to get the desired melt time.
It is possible to use a means for adjusting. For this
Is a mixture of any of the conventionally known hardeners.
It can also be used.   That is, for example, chromium salts (chromium alum, chromium acetate, etc.)
Aldehydes (formaldehyde, glyoxa
, Glutaraldehyde, etc.), N-methylol compound
Products (dimethylol urea, methylol dimethyl hydantoi
), Dioxane derivatives (2,3-dihydroxydio)
Active vinyl compounds (1,3,5-triacrylic acid)
Royl-hexahydro-2-triazine, 1,3-vinyl
Such as sulfonyl-2-propanol), active halogenation
Compound (2,4-dicrol-6-hydroxy-3-tria
Gin, etc.), mucohalic acids (mucochloric acid, mukov
Enokicyclo acid etc.) and the like can be used.   Hardeners preferably used are aldehyde compounds, eg
For example, formaldehyde, glyoxal, S-triazine
Compounds such as 2-hydroxy-4,6-dichloroto
Riazine sodium salt, vinyl sulfone compound, etc.
You.   The amount of the hardening agent used is a hardening accelerator or hardening inhibitor, etc.
Is affected by the presence of^-6Mo
Le / g / gelatin ~ 1 x 10^-2For mol / g / gelatin
Can be. More preferably 5 × 10^-FiveMol / g gelatin
~ 5 × 10^-3Used in mol / g gelatin.   Representative specific examples of hardeners that can be used below
However, the present invention is not limited thereto.
No. Typical hardener examples   HCHO   CH_ThreeCHO   OHCCH_{Two Three}CHO   ClCH_TwoCONHCOCH_TwoCl   ClCH_TwoCOOCH_TwoCH_TwoOOCCH_TwoCl   CH_ThreeCOCl CH_ThreeCOCH_TwoCl   CH_Two= CHSO_Three(CH_Two)_ThreeSO_TwoCH = CH_Two   C (CH_TwoSO_TwoCH = CH_Two)₄   CH_Two= CHCOOCOCH = CH_Two   CH_Two= CH-O-CH = CH_Two   The wet film thickness at the time of application of the light-sensitive material of the present invention is preferably
The range of 35 to 85 μm is suitable, but more preferably 40 to
75 μm range, most preferably 47-70 μm
You. If the wet film thickness is too thick, the load during drying will increase.
Therefore, it is necessary to take measures such as increasing the drying heat quantity and decreasing the coating speed.
May decrease the production cost, productivity, etc.
I will. On the contrary, if the wet film thickness is too thin, there will be no failure and uniform application.
Can be difficult.   The wet film thickness referred to in the present specification is one kind or two or more kinds.
When coating the coating solution on the support in multiple layers at the same time,
Immediately after applying these coating solutions (in other words, before drying begins
(State) means the total thickness (μm) of the film in the wet state. This
The wet film thickness (μm) of is calculated by the following formula. That is, Wet film thickness (μm) = (total amount of coating liquid supplied (L / min.) × 1000) / (Coating speed (m / min.) × Application width (m)) Is required.   In addition, the wet film thickness referred to in this specification means that the coating is obtained by the following formula.
If it is applied, that is, after application and drying, further application is performed on it.
If so, the thickness of the coating liquid for each coating
Say only   In the practice of the present invention, the silver halide emulsion layer is
Compounds represented by the general formulas [I], [II] and [III]
It is possible to add at least one sensitizing dye selected from
preferable.   The general formulas [I], [II] and [III] are as shown below.
is there.   General formula(Where R₁, R_Two, R_ThreeIs a substituted or unsubstituted alkyl
Represents a group, an alkenyl group or an aryl group, and at least
R₁And R_ThreeOne of these is a sulfoalkyl group or carxial
Take the kill group. X₁ ^-Is an anion, Z₁And Z_TwoIs a substitution or
The group of non-metal atoms required to complete an unsubstituted carbocycle, n is
Represents 1 or 2. (However, when forming an inner salt
n is 1. )] (R in the formula_Four, R_FiveIs a substituted or unsubstituted alkyl group,
Represents an alkenyl group or an aryl group, and at least R_FourWhen
R_FiveEither of these is a sulfoalkyl group or
Take the rukyru group. R₆Is hydrogen atom, lower alkyl group, ant
Group. X_Two ^-Is an anion, Z₁And Z_TwoIs a substitution or
The group of non-metal atoms required to complete an unsubstituted carbocycle, n is
Represents 1 or 2. (However, when forming an inner salt
n is 1. )] (R in the formula₇And R₉Is a substituted or unsubstituted lower alkyl
Group, R₈And R_TenIs a lower alkyl group, hydroxyalkly
Group, sulfoalkyl group, carboxyalkyl group, X_Three ^-
Is an anion, Z₁And Z_TwoCompletes a substituted or unsubstituted carbocycle
The group of non-metal atoms necessary for formation, n is 1 or 2.
(However, n is 1 when forming an intramolecular salt.)]   Z in each formula₁, Z_TwoThe carbocycle that completes
Is preferably an aromatic ring such as an unsubstituted benzene ring or naphthalene ring.
Good.   Also, in the formula [I], X₁ ^-As an anion represented by
Is, for example, chlorine ion, bromide ion, iodine ion, thiol
Cyanate ion, sulfate ion, perchlorate ion, p-to
Examples include ruene sulfonate ion, ethyl sulfate ion, etc.
be able to.   Next, typical components of the compound represented by the general formula [I]
Examples of the body are shown below, but the present invention is not limited thereto.
is not.   In the formula [II], R₆Is a hydrogen atom, a lower alkyl group,
It represents an aryl group, and a lower alkyl group is a methyl group.
And groups such as ethyl, ethyl, propyl and butyl. A
Examples of reel groups include, for example, phenyl groups.
You. R_FourAnd R_FiveIn the explanation of the above formula [I],
R in formula [I]₁, R_ThreeCan be listed as
Wear. X_Two ^-Of the formula [I]₁ ^-Illustrated as
Things can be mentioned.   Next, typical examples of the compound represented by [II] will be given.
However, of course, the present invention is limited by this example also in this case.
Not something.   Next, in the formula [III], R₇, R₉Lower alkyl group of
Examples include groups such as methyl, ethyl, propyl, butyl, etc.
Can be shown. The substituted alkyl group is represented by the formula [I]
R₁~ R_ThreeThe groups exemplified above can be mentioned. R₈, R_Ten
The lower alkyl group of is R₇, R₉The same thing can be illustrated. Ma
R₈, R_TenHydroxyalkyl group, sulfoalkyl group,
The carboxyalkyl group is represented by R in the formula [I].₁~ R_Three
The groups exemplified above can be mentioned.   X_Three ^-The anion of is also the formula X₁ ^-Listed as
be able to.   Representative specific examples of the compound represented by the formula [III]
Are listed below. Of course, even in this case, the present invention
It is not limited. (Compound example)   Of the compounds represented by the above formulas [I], [II] and [III]
The total amount added is 100 mg to 2000 mg per mol of silver halide.
Can be used. Especially 400mg-1000mg
preferable.   In addition, the compounds represented by the above formulas [I], [II] and [III]
The position of addition of the substance may be any position during the production of the photosensitive material.
Before chemical aging, during chemical aging, at the end of chemical aging, or
Addition just before coating is preferable.   The photographic emulsion used in the present invention includes a photosensitive material manufacturing process.
Prevent fogging during storage or photo processing
Or various compounds for the purpose of stabilizing photographic performance.
You can have it. That is, azoles such as
Zonthiazolium salts, nitroimidazoles,
Nsimidazoles, chlorobenzimidazoles,
Lomobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimi
Dazoles, mercaptothiadiazoles, aminotri
Azoles, benzotriazoles, nitrobenzotris
Azoles, mercaptotetrazoles (especially 1-phenyl)
Nil-5-mercaptotetrazole) and the like; mercapto
Pyrimidines; mercaptotriazines; for example oxa
Thioketo compounds such as drinthione; Azoindene
, Eg triazaindene, tetraazaindenes
(Especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaine
Benzenes), pentaazaindenes, etc .; benzenethios
Rufonic acid, benzenesulfinic acid, benzenesulfon
As an antifoggant or stabilizer such as acid amide
Many known compounds can optionally be added.   For details, see Stabilization of E.J.Birr.
・ Photographic silver halide halide
(Stabilization of Photographic Silver Halid
e Emulsions), Focal Press, 1974
No.   Compounds that can be used are, for example, U.S. Pat.No. 2,131,038
And thiazoliu described in No. 2,694,716, etc.
Salt; US Patent Nos. 2,886,437 and 2,444,605
Azaindenes described: U.S. Pat. No. 3,287,135
, Etc .: U.S. Pat. No. 3,23.
Sulfocatechols described in No. 6,632: UK
Oximes described in Japanese Patent No. 623,448;
U.S. Pat.Nos. 2,403,927, 3,266,897, 3,397,
Mercaptotetrazole described in 987 etc.
, Nitrones: Nitroindazoles: US Pat. No. 2,83
Polyvalent metal salt described in 9,403 etc.
tal snlts): described in US Pat. No. 3,220,839
Thiuronium Salts: US Patent No.
No. 2,566,263, No. 2,597,715, etc.
Radium, platinum and gold salts.   The light-sensitive material of the present invention comprises a hydrophilic colloid layer and a filter.
As a dye, prevention of irradiation, halation
Water-soluble dye for various purposes such as
No. Such dyes include oxonol dyes and hemioxo dyes.
Nord dye, styryl dye, merocyanine dye, cyan
And azo dyes. Oxonol
Dyes; with hemioxonol dyes and merocyanine dyes
It is for.   In the light-sensitive material of the present invention, a dye is added to the hydrophilic colloid layer.
And UV absorbers are included, they are
It may be mordanted by an on polymer.   Such disclosures include Research Disclosure
ー, Volume 176, Absorbing and Filling, P23-26
Tar soybean (Absorbing and filter dyes)
The ones listed are used.   In the photographic emulsion layer of the photographic light-sensitive material of the present invention, sensitivity is increased,
In order to increase trust or accelerate development, for example, poly
Alkylene oxide or its ethers, esters,
Derivatives such as min, thioether compounds, thiomorpho
Phosphorus, quaternary ammonium salt compound, urethane derivative,
Urea derivative, imidazole derivative, 3-pyrazolidones
Etc. may be included.   The photographic light-sensitive material of the present invention includes a photographic emulsion layer and other hydrophilic materials.
Insoluble in water for the purpose of improving the dimensional stability of the aqueous colloid layer
Or can contain a dispersion of poorly soluble synthetic polymer
You. For example, alkyl (meth) acrylate, alkoxy
Alkyl (meth) acrylate, glycidyl (meth) a
Acrylate, (meth) acrylamide, vinyl ester
(Eg, vinyl acetate), acrylonitrile, olefin
Or styrene, alone or in combination, or
Lato acrylic acid, methacrylic acid, α, β-unsaturated dicar
Boric acid, hydroxyalkyl (meth) acrylate, su
Rufoalkyl (meth) acrylate, styrene sulfone
Do not use a polymer that uses a combination of acids as the monomer component.
Can be. The term (meth) acrylate above means
Abbreviated both acrylate and methacrylate
Things.   A protective layer is preferred for the silver halide photographic light-sensitive material of the present invention.
This protective layer is made of hydrophilic colloid.
And the hydrophilic colloid used is as described above.
Is used. Even if the protective layer is a single layer,
It may be a layer.   The emulsion layer or the protective layer of the silver halide photographic light-sensitive material of the present invention.
In the protective layer, preferably in the protective layer, a matting agent and / or
Alternatively, a leveling agent or the like may be added. Public as a matting agent
Known ones can be used, but more preferably polymer map
The average particle size is preferably 0.3 μm to 12 μm.
Especially, those in the range of 3 μm to 9 μm are preferable.   In carrying out the present invention, the polymer matting agent used
Specific examples include polymethylmethacrylate.
When water-dispersible vinyl polymer and cellulose acetate
Propionate, starch, etc. are used. Especially methyl
Taacrylate, glycidyl acrylate, glycidyl
Single weight of acrylic ester such as methacrylate
Combined, or these acrylates or other vinyl
Water-dispersible vinyl polymer such as copolymer with vinyl monomer
Matting agents are preferred. Among them, polymethylmethacrylate
A spherical matting agent having an average particle diameter of 3 to 9 μm is particularly preferable.
preferable.   The matting agent is added at the protective layer above the emulsion layer or
For example, it is added to the protective layer on the back side, but
It is more preferable to add the coating agent to the protective layer on the emulsion layer side.
For example, using a roller carrier type automatic developer,
When processing a photographic light-sensitive material containing a hardener, the light-sensitive material
Will not slip.   Smoothing agent helps prevent adhesive failure similar to matting agents
Others, especially when projecting or projecting motion picture film
It is effective in improving the friction characteristics related to
Typical examples are liquid paraffin and esters of higher fatty acids.
Waxes such as type, polyfluorinated hydrocarbons
Or its derivatives, polyalkyl polysiloxane, poly
Aryl polysiloxane, polyalkyl aryl poly
Roxane or alkylene oxide addition thereof
Silicones such as derivatives are preferably used.
You.   The light-sensitive material of the present invention can be applied to prevent fog during coating and drying.
Prevention of fogging and desensitization due to bending under low humidity conditions
Therefore, it is preferable to use a plasticizer. As a plasticizer
For example, Japanese Patent Laid-Open No. 48-63715, Japanese Patent No. 43-4939,
No. 47-8745, U.S. Patents 306,470, 2,960,404, and
Use those listed in 3,412,159, 3,791,857, etc.
However, at least a melting point of 40 ° C. or higher is preferable.
Use fewer polyhydric alcohol compounds with two or more hydroxyl groups.
It is to contain at least one kind. Such a compound
Has 2 to 12 hydroxyl groups and 2 to 20 carbon atoms.
And the hydroxyl groups are conjugated with a conjugated chain.
No alcohol, i.e. alcohol that can't write the oxidized form is preferred
No. Further, the melting point is preferably 50 ° C or higher and 300 ° C or lower.
New Examples of compounds are described in JP-A-62-147449.
There is   In carrying out the present invention, the light-sensitive material has various uses.
Surfactants can be used for this purpose, for example saponin
Teroids), alkylene oxide derivatives (for example,
Polyethylene glycol, polyethylene glycol / poly
Propylene glycol condensate, polyethylene glycol
Alkyl ethers or polyethylene glycol
Killaryl ethers, polyethylene glycol s
Tells, polyethylene glycol sorbitan ester
, Polyalkylene glycol alkylamine or
Polyimide oxide adducts of amides and silicones
), Glycidol derivatives (eg alkenyl succinic acid)
Polyglyceride, alkylphenol polyglyceride
De), fatty acid esters of polyhydric alcohols, sugar alky
Non-ionic surfactants such as polyesters
You. In addition, alkyl carboxylate, alkyl sulfone
Acid salt, alkylbenzene sulfonate, alkyl naphth
Tarensulphonate, alkyl sulfates, al
Killyl phosphates, N-acyl-N-alkyl tau
Phosphorus, sulfosuccinates, sulfoalkyl
Lioxyethylene alkyl phenyl ethers, Polio
Such as xylene ethylene alkyl phosphates,
Carboxy group, sulfo group, phospho group, sulfate ester group,
Anionic surfactant containing acidic group such as phosphate group
Etc. can be used. Further amino acids, aminoal
Killsulfonic acid, aminoalkyl sulfuric acid or phosphoric acid
Steals, alkyl betaines, amine oxides, etc.
And amphoteric surfactants. Also alkyl amine
Salts, aliphatic or aromatic quaternary ammonium salts,
Heterocyclic quaternary annes such as pyridinium and imidazolium
Monium salts, and phosphonic compounds containing aliphatic or heterocyclic rings
Cationic surfactants such as um or sulfonium salts
Is mentioned. In addition, fluorine-containing surfactant, polyoxy
It is possible to use a fluorine-containing surfactant having a thylene group.
it can.   As the alkylene oxide-based surfactant, Japanese Patent Publication No.
-9610, DT-2648746, JP-A-53-129623, 54-8962
4, the same 54-98235, the same 58-203435, the same 58-208743, the same 60-
80848, 60-94126 and the like. Alkyleneoxy
Examples of combined use of a de-surfactant and other compounds include:
JP-A-54-89626, 55-70837, 57-11341, 57-1
09947, 59-74554, 60-80839, 60-80846, 50
-131293, 53-29715 and the like.   As anionic surfactants, JP-A-53-21922, GB
-1503218, Japanese Patent Publication No. 56-1617, and sulfuric acid of higher alcohols
Ester salts, higher alkyl sulfonates, alkylbens
Zen sulfonate, dialkyl sulfosuccinate, a
Sylmethyl tauride, N-acyl sarcosinate, fat
Acid monoglyceride sulfate, α-sulfonic acid, etc.
No.   As the fluorine-containing surfactant, for example, Japanese Patent Publication No. 47-930
3, 48-43130, 52-25087, 57-1230, JP-A-49
-46733, 50-16525, 50-34233, 51-32322, 51-322322
54-14224, 54-111330, 55-557762, 56-1904
2, the same 56-41093, the same 56-34856, the same 57-11341, the same 57-29
691, 57-64228, 57-146248, 56-114944, 56
-114945, 58-196544, 58-200235, 60-10954
8, Same 57-136534, US-3589906, Same-3775126, Same-429
2402, RD-16630, and other compounds disclosed,
The compounds exemplified in 60-164738 are listed.
You.   The photographic light-sensitive material of the present invention may contain various other materials as necessary.
Can be used. For example, dye, development
Accelerators, optical brighteners, antifoggants, UV absorbers,
What is it? Specifically, Research Disclosure
(RESEARCH DISCLOSURE) 176 pages 22-31 (RD-17643,
1978) can be used.   The silver halide photographic light-sensitive material of the present invention additionally requires
Depending on the antihalation layer, intermediate layer, filter
Layers and the like can be provided.   Photographic emulsion layer and other layers in the photographic material of the present invention
Is a flexible support commonly used in photographic photosensitive materials.
Can be embodied coated on one or both sides
You. A useful flexible support is cellulose nitrate.
, Cellulose acetate, cellulose acetate butyrate, polystyrene
, Polyvinyl chloride, polyethylene terephthalate,
A film made of a semi-synthetic or synthetic polymer such as carbonate
Film, variator layer or α-olefin polymer (eg
For example, polyethylene, polypropylene, ethylene / butene
(A copolymer) or the like.
The support may be colored using a dye or a pigment. Shading
It may be black for the purpose. The surface of these supports is
Generally, a subbing treatment is applied to improve adhesion with photographic emulsion layers.
It is. As the undercoat treatment, the technique described in Japanese Patent Application No. 60-25704 is used.
It is preferable to use surgery. The surface of the support is undercoated
Before or after corona radiation, UV irradiation, flame treatment etc.
May be applied. See Research Disclosure for details.
-For those listed in "Supports" on page 25, Volume 176,
Can be.   In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other
The hydrophilic colloid layer can be applied on the support or by various coating methods.
Can be applied on other layers. For coating, use the deep coating method,
Roller coating, curtain coating, extrusion coating, etc.
Can be. For details, see Research Disclosure.
176, pp. 27-28, "Codting procedures" section
Can be used.   Specific examples of the silver halide photographic light-sensitive material of the present invention include
Xray photosensitive material, squirrel photosensitive material, black and white photography photosensitive material,
Color reversal photographic material, color photographic paper, colloid tran
Shur process, silver salt diffusion transfer process, Daitra
Hair process, silver dye bleaching method, printout feeling
It can be used as a material, a photosensitive material for heat development, and the like.   Exposure to obtain a photographic image can be done using conventional methods.
I just need. That is, natural light (sunlight), tungsten
Lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp
Lamp, xenon flash lamp, cathode ray tube flying spot
Light emitting diode, laser light (eg gas laser
ー, YAG laser, dye laser, semiconductor laser
Do not use any of various light sources including ultraviolet light.
Can be. Also, by electron beam, X-ray, γ-ray, α-ray, etc.
Exposed by the light emitted from the excited phosphor
Is also good. Is the exposure time 1/1000 second usually used in cameras?
Exposure time of less than 1/1000 second, as well as exposure time of 1 second, eg
For example, 1/10 using a xenon flashlight or cathode tube^Four~ 1/10⁶Seconds
Exposure can be used, or exposure longer than 1 second
You can also. For color exposure if necessary
The spectral composition of the incoming light can be adjusted.   For photographic processing of the light-sensitive material of the present invention, for example, research
Research Disclosure No. 176, No. 25
−30 (RD-17,643)
The method and any of the various treatment solutions can be applied
You. This photographic process forms a silver image, depending on the purpose
Photographic processing (black and white photographic processing), or forming a dye image
Any of photographic processing (color photographic processing) may be used.
The treatment temperature is usually selected between 18 ° C and 50 ° C, but 18 ° C
The temperature may be lower or higher than 50 ° C.   In addition, depending on the case, other various developing methods (for example,
Thermal development) can be used.   For example, the developer used for black and white photographic processing is
The developing agent may be included. As a developing agent
For example, dihydroxybenzenes (for example, hydroquinone
), 3-pyrazolidones (eg 1-phenyl-3-
Pyrazolidone), aminophenols (eg N-methyl)
Or p-aminophenol), etc., alone or in combination.
It can be used together. Other types of developer are generally
Preservatives, alkali agents, pH buffers, antifoggants, etc.
And, if necessary, dissolution aids, toning agents, and development acceleration
Agent, surfactant, defoaming agent, water softener, hardener, with viscosity
You may also include a prescription agent.   As a special form of development processing, the developing agent is a photosensitive material.
Medium, for example, in the emulsion layer, the light-sensitive material contains an alkaline aqueous solution.
You may use the method of processing in and making it develop. developing
Hydrophobic base drugs are available from Research Disclosure
169 (RD-16928) U.S. Patent No. 2,739,890, United Kingdom
Patent No. 813,253 or West German Patent No. 1,547,763
It can be incorporated into the emulsion layer in the various ways described.
Such a development process makes the silver salt stable with thiocyanate.
It may be combined with a chemical treatment.   As the fixer, use a commonly used composition.
Can be As a fixing agent, thione sulfate, thiol
Besides cyanate, it is known to be effective as a fixing agent
Organic sulfur compounds can be used. The fixer is hard
A water-soluble aluminum salt may be included as a film agent.   A color-forming coupler is used in the photographic emulsion layer of the photographic light-sensitive material of the present invention.
-That is, aromatic primary amines are present in color development processing
Imaging agents (for example, phenylenediamine derivatives and
Generated by oxidative coupling with enol derivatives, etc.)
A colorable compound may be included. For example, magenta cap
5-pyrazolone coupler, pyrazolobenz
Imidazole coupler, cyanoacetyl tamaron coupler
, Open-chain acylacetonitrile coupler, etc.
As a low coupler, an acylacetamide coupler (eg
For example, benzoylacetanilides, pivaloylacetoa
Nilide), etc., and as a cyan coupler, naphtho
Lu coupler, phenol coupler, and the like. this
These couplers are hydrophobic groups called ballast groups in the molecule.
A non-diffusible type having a is preferable. Coupler is silver ion
Either 4 equivalents or 2 equivalents
No. Also, a colored coupler that has the effect of color correction, or
Is a coupler that releases a development inhibitor with development.
DIR coupler).   In addition to the DIR coupler, it also produces coupling reactions.
Colorless DIR cover that is colorless and releases a development inhibitor.
A pulling compound may be included.   The silver halide photographic light-sensitive material of the present invention prevents color fog
As agents, hydroquinone derivatives, aminophenol derivatives
Contains conductors, gallic acid derivatives, ascorbic acid derivatives, etc.
May have.   The silver halide photographic light-sensitive material of the present invention comprises a hydrophilic roller.
The id layer may include an ultraviolet absorber. For example, Ally
Benzotriazole compounds substituted with a phenyl group (eg rice
Those described in Japanese Patent No. 3,533,794), 4-thiazolidone
Compounds (for example, in U.S. Pat. Nos. 3,314,794 and 3,352,651)
Those described), benzophenone compounds (for example, JP-A-46
-2784), cinnamic acid ester compounds (eg
For example, those described in U.S. Patents 3,705,805 and 3,707,375
), Butadiene compounds (eg, US Pat. No. 4,045,229)
), Or a benzooxide compound
(Eg, those described in US Pat. No. 3,700,455)
be able to. Further, U.S. Pat.
Those described in No. -48535 can also be used. UV rays
Absorptive coupler (for example, α-naphthol cyan color)
(Former-forming coupler), UV absorbing polymer, etc.
May be. These UV absorptions are mordanted to specific layers.
It may be.   When carrying out the present invention, various anti-fading agents are used in combination.
It is also possible to use an optional color image stabilizer alone or in combination with 2.
It is also possible to use together more than one species. As an anti-fading agent,
Idroquinone derivative, gallic acid derivative, p-alkoxy
Phenols, p-oxyphenol derivatives and bisiffs
There are enols, etc.   Color developers generally contain an alkali containing a color developing agent.
It consists of an aqueous solution. Color developing agents are various primary aromatic compounds
Amine developers such as phenylenediamines (eg 4
-Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-E
Cyl-N-β-hydroxyethylaniline, 3-methyl
-4-amino-N-ethyl-N-β-hydroxyethyl
Aniline, 3-methyl-4-amino-N-ethyl-N-
β-Methanesulfoamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylanili
Etc.) can be used.   In addition, L.F.A.Mason, Photographic Process
Sing Chemistry (Photographic Processing Chem
istry), published by Focal Press, 1966, P226-229, US special
No. 2,193,015, No. 2,592,364, and JP-A-48-64933.
Any of those described may be used.   Other color developers include alkali metal sulfites and charcoal.
PH buffers such as acid salts, borates, and phosphates, bromide
Substances, iodides, and development inhibitors such as organic antifoggants.
An antifoggant or the like may be included. Also needed
Depending on the type, water softener, such as hydroxyaluminum
Agents, benzyl alcohol, diethylene glycol, etc.
Organic solvent, polyethylene glycol, quaternary ammonium
Development accelerators such as salts and amines, color dye forming couplers,
Conflict coupler, turnip like sodium boron hydride
Auxiliary agents such as stimulants, 1-phenyl-3-pyrazolidone
Image agent, viscosity imparting agent, polycarboxylic acid chelating agent, oxidation
Inhibitors may be included.   The photographic emulsion layer after color development is usually bleached. Drift
The white processing may be performed at the same time as the fixing processing or individually.
May be done. Examples of bleaching agents include iron (III),
Multivalent such as cobalt (III), chromium (VI), copper (II)
Metal compounds, peracids, quinones, nitroso compounds, etc.
Used.   For example, Pherician compounds, dichromates, iron (II
Organic complex salts of I) or cobalt (III), eg ethylene
Diamine tetraacetic acid, nitrolylotriacetic acid, 1,3-diamino
-2-Propanol tetraacetic acid and other aminopolycarboxylic acids
Of organic acids such as citric acid, tartaric acid, malic acid, etc.
Complex salts, persulfates; permanganates; nitrosophenols
Etc. can be used. Of these, Phenilithia
Potassium chloride, ethylenediaminetetraacetate iron (III) sodium
And ethylenediaminetetraacetic acid iron (III) ammonium
Is particularly useful. Ethylenediaminetetraacetic acid iron (III)
The complex salt does not smell in the one-bath bleach-fixing solution even in the independent bleaching solution.
It is also useful. 〔Example〕   Hereinafter, embodiments of the present invention will be described in detail. Of course,
However, the present invention is limited to the embodiments described below.
It is not something to be done. Example-1   While controlling to 60 ° C, pAg = 8.0 and pH = 2.0,
2.0 mol% of silver iodide with a flat grain size of 0.20 μm by the Blujet method
A short-dispersion cubic crystal emulsion of silver iodobromide containing was obtained. One of this emulsion
The part was used as a core and grown as follows. That is
Solution containing core particles and gelatin at 40 ℃ and pAg 9.0
It contains a monic silver nitrate solution, potassium iodide and potassium bromide.
Solution and double-jet method to add silver iodide to 30 mol%
A first coating layer containing was formed. And further pAg = 9.0, pH =
At 9.0, add ammoniacal silver nitrate solution and potassium bromide solution
Add by the double jet method to form the second coating layer, average
A cubic crystal short dispersion silver iodobromide emulsion having a grain size of 0.50 μm was prepared, and E
It was set to -1. The average silver iodide content of this emulsion is 2.2 mol%
there were.   In the same manner as in E-1, ammoniacal silver nitrate solution and ha
Same composition as E-1 by changing the addition time and flow rate of the ride solution
Emulsion E-2 having an average grain size of 0.65 μm
Emulsion E-3 having a silver halide content of 2.0 mol% and an average grain size of 1.0 µ
Were prepared respectively.   Further, a polydisperse emulsion E-4 was prepared by the normal mixing method.
That is First, four kinds of solutions are prepared.   Inject liquid B and liquid C into the reaction kettle for emulsion preparation and rotate at 30 rpm.
Stir with a propeller stirrer at 0 revolutions / minute and set the reaction temperature to 60.
C. Next, divide solution A into 1 volume: 2 volumes, and
One volume of 100 ml was added over 1 minute. 5 minutes
After continuing to stir for 2 minutes, add 200 ml of the remaining 2 volumes of solution A to 2
It was added over a period of 1 minute, and stirring was continued for another 15 minutes. And
Add solution D to adjust the pH of the solution in the reaction kettle to 6 and react
Was stopped. In this way, polydisperse emulsion E-4 was obtained.
Was. This emulsion contains 2.0 mol% of silver iodide and has an average grain size of
The diameter was 1.00 μm.   Chloroauric acid for E-1, E-2, E-3, E-4
Salt, sodium thiosulfate, ammonium thiocyanate
In addition, gold-sulfuric acid sensitization was optimally performed, and then the above-exemplified sensitization was performed.
Add the amounts of color-sensing dyes (43) and (74) described below, and add 4-hydr
Roxy-6-methyl-1,3,3a, 7-tetrazaindene 2 ×
Ten^-2Stabilized in moles.   In addition, each emulsion is processed by a conventional coagulation method before chemical sensitization.
Desalting was performed. That is, keep at 40 ℃, naphthalene sulfonic acid
Sodium formalin condensate and magnesium sulfate water
The solution was added to cause aggregation. After removing the supernatant,
Add pure water, then add magnesium sulfate aqueous solution again to agglomerate.
And the supernatant was removed.  Trace of chemical sensitization, mixed in combinations as shown in Table-1
Then, the gelatin amount shown in Table 1 was adjusted. Emulsion and preservation
Add the following additives to the protective membrane solution and add melty
The hardener (Formua)
Ludehid) and (glyoxal) mixed in equimolar
added.   Add the following additives to the emulsion and overcoat solution respectively.
Was.   That is, as an emulsion layer additive, per mol of silver halide
t-Butyl-catechol 400mg, polyvinylpyrrolidone
(Molecular weight 10,000) 1.0g, Styrene / maleic anhydride co-weight
Combined 2.5 g, polyethyl acrylate (molecular weight 250,000) 2.
5g, trimethylolpropane 10g, diethylene glycol
5 g, nitrophenyl-triphenylphosphonium
Chloride 50 mg, 1,3-dihydroxybenzene-4-su
Ammonium ruphonate 4g, 2-mercaptobenzimida
Zol-5-sodium sulfonate 15mg, 2-mercaptobe
Nutthiazole 10 mg, 1,1-Dimethylol-1-bromo-1-nitromethane 1
0 mg, Etc. were added.   In addition to the above emulsion, various additives described below are added in Table 1.
Apply the protective layer with the indicated gelatin amount by the slide hopper method.
Simultaneously on both sides of the polyester film support that has been subbed
And the silver halide emulsion layer (viscosity 11 cp, surface
Surface tension 35dyn / cm, coating film thickness 50μm, protective layer (viscosity 11cp,
Surface tension 25 dyn / cm, coating film thickness 20 μm) coating speed 60 m / min
Then, two layers were simultaneously coated in layers to obtain a sample. How much silver
45 mg / dm^TwoMet.   The following compounds were added as protective layer additives. That is
Per 1 g of gelatin, 10 mg, 2 mg, C₉F₁₉-OCH_TwoCH_TwoO_TenCH_TwoCH_TwoOH 2mg, C₈F₁₈SO_ThreeK 3mg, A machine made of polymethylmethacrylate having an average particle size of 5 μm
7 mg, 70 mg of colloidal silica with an average particle size of 0.013 μm Etc. were added.   For each sample, measure the sensitivity and fog as follows.
I went to. That is, two samples with the concentration gradient matched in mirror symmetry
It is sandwiched between the optical wedges of the
And simultaneously expose the same amount for 1 / 12.5 seconds.   The processing follows the following steps, and the total processing time is 45 seconds.
Performed using the roller transfer type automatic processor shown in the figure.
Was.             Processing temperature Processing temperature Insertion --- 1.2 seconds Development + migration 35 ℃ 14.6 seconds Fixation + migration 35 ℃ 8.2 seconds Washing + crossing 25 ° C 7.2 seconds Squeeze 40 ℃ 5.7 seconds Dry 45 ℃ 8.1 seconds Total −− 45.0 seconds   The following developer and fixer were used.   From the obtained characteristic curve, base density + fog density + 1.0
The exposure amount at
The degree and granularity were evaluated. In FIG. 1, 1 is a film
Insertion table, 2 is a film basket, 3 is an operation panel, 31
Is a remote control receiver, 4 is a roller, 5 is a transport path, and 6 is a current
Image liquid tank, 7 is a fixing tank, 8 is a washing tank, 9 is a drying section, and 91 is a soot.
Quiz rack, 92 is a drying rack.   By mixing the emulsion grains as in this example,
, An arbitrary sensitometric curve as shown in Fig. 3 can be obtained.
In addition, ultra-rapid processing is possible. <Developer>   1 solution and potassium hydroxide solution with pH 10.50
did. <Fixer>  Make the aqueous solution of 1 and add glacial acetic acid to make a solution of pH 4.0.
Was.   The graininess was evaluated as follows. Under the above processing conditions,
Concentration of samples processed using a roller transport type automatic processor
The degree of roughness of developed silver particles at 1.0 is visually evaluated.
Was. It is represented by a 5-step display from 1 (poor) to 5 (excellent). 3-5
There is no problem in, but 1-2 is not practical.   Fog was also measured. About this, 7 days after application
Fog and 55 ° C, 30RH, 3 days as a substitute evaluation for aging
The fog after the heat treatment during the period was also obtained.   The dryness was evaluated as follows. That is 45 seconds above
After the automatic development process, the samples that have passed through the dry area are processed.
The texture, and the degree of Kutuki with other samples.
It was evaluated and expressed in a 5-step scale of 1 (poor) to 5 (excellent). 3
No problem occurs in -5, but practical use is not acceptable in 1-2.   For each sample, the line of the above 45-second automatic processor is
・ Reduced speed to 1/2 and the sensitivity of conventional 90 seconds processing
I asked. The above results are shown in Table 1.   As is clear from Table 1, the sample according to the present invention has a time of 45 seconds.
When subjected to ultra-rapid treatment of
Excellent in yellowing, and sensitivity is reduced in comparison with processing in 90 seconds
Less, processing time is cut in half and there is no problem, super quick
You can see that it can be processed quickly. Example-2   Silver iodide was prepared in the same manner as in the preparation of Emulsion E-4 of Example-1.
Polydisperse emulsion E-5 containing 2 mol% and having an average particle size of 0.65 μ
I got Then, it was chemically sensitized in the same manner as in Example-1.
The added sensitizing dye and its amount are the same as those of E-2.
is there.   Emulsions E-1 to E-5 were used and averaged as a protective layer additive.
A map made of polymethylmethacrylate with a particle size of 3.5 μm.
A sample was prepared in the same manner as in Example 1 except that the coating agent was used.
Was. However, as the melting time is shown in Table-2,
Hardener was added.   These samples were processed in the same manner as in Example-1, and the sensitivity and
Burr, graininess, and dryness were evaluated. The sensitivity is sample No. 3
The relative sensitivity was expressed with 7 being 100.   The pressure desensitization was measured as follows. Ie pressure
Desensitization was performed after conditioning each sample for 5 hours at 23 ° C and 30% RH.
It was bent about 280 degrees with a radius of curvature of 2 cm below. 3 minutes after bending
Then, the X-ray exposure is performed in the same way as the sensitivity measurement, and the above 45 seconds is automatically
A development process was performed.   Desensitized area caused by bending at a blackening density of 1.0
Difference ΔD between the density of 1.0 and the density of the part not bent
It was expressed by. That is, the smaller this value, the smaller the pressure desensitization.
And   The water content was also measured according to the procedure described above. That is,
Sufficiently remove the sample when it exits the quiz rack 91
After drying, leave for 1 hour or more at 25 ° C 55% RH
And measure its weight. W this_d(G). Water content
The amount is calculated from the following formula. Water content (g / m^Two) = (W_w-W_d) × (10000 cm^Two/ 20cm × 20cm)   As is clear from Table-2, the sample according to the present invention is 45 seconds
When processed with, sensitivity, fog, pressure desensitization, graininess, dryness
It can be seen that the properties are excellent. Further, the sample according to the present invention
Among them, the melting time is 15 to 30 minutes and the water content is 9 to
14g / m^Two(Sample No. 36, 37, 46, 47, 50 to 52, 18, 25, 65, 6
It can be seen that 6) is particularly suitable for ultra-rapid processing. Example-3   In the same manner as in Example-1, as shown in Table 3 below.
Monodisperse emulsions E-6 to E-13 having an average particle size were prepared.   The average silver iodide content of each emulsion is 2.0 mol%.
is there. The above emulsion was chemically sensitized in the same manner as in Example-1.
The amount of sensitizing dye added is shown in Table-4.   Examples using the above emulsions E-6 to E-13 and E-4
As in 1, add emulsion layer additives and protective film additives to obtain coating liquid.
Was prepared and applied to obtain a sample. However, the emulsion of this time
The combinations are as shown in Table-5. Melty of all samples
Longing time is 25 minutes, gelatin amount is 3.00 (g / m per side)^Two)
It is.   The obtained sample was treated in the same manner as in Example-1 to obtain
The characteristic curve is shown in Fig. 2. Sensitivity, γ (point at density 1.0 and density 2.0
If the slope of the straight line connecting the points is θ, then tan θ is γ
Yes, and granularity is shown in Table-5. The sensitivity is sample No. 79.
The relative sensitivity was shown as 100.   From Table-5 and FIG. 2, according to a preferred embodiment of the present invention.
Sample Nos. 79-83 used by mixing certain emulsions were processed for 45 seconds
So, there is no problem with sensitivity, γ, graininess, and sensitometry
The Lee curve is smooth and the amount of information obtained is large. The present invention
No. 78, which is outside the preferred embodiment of
The amount of information that can be obtained is small (especially the legs). Also 7 or more kinds of grains
No. 84 and 85, which consist of children, have a low γ after 45 seconds of treatment, resulting in graininess.
Inferior and the sensitometric curve is not smooth.〔The invention's effect〕   As described above, when the light-sensitive material of the present invention is rapidly processed
Sensitivity, fog, pressure desensitization, graininess, dryness, etc.
It has excellent sex.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram showing an example of an automatic processor which can be used in the embodiment of the present invention. FIG. 2 is a diagram showing characteristic curves of photosensitive material samples prepared in Examples. FIG. 3 is a diagram showing an example of the characteristic curve. 1 ... Film insertion table, 2 ... Film basket, 3
... Operation panel, 31 Remote control receiver, 4 Roller, 5 Transport path, 6 Developer tank, 7 Fixing tank, 8
…… Rinse tank, 9… Drying section, 91 …… Squeeze rack, 92
...... Dry rack.

   ────────────────────────────────────────────────── ─── Continuation of front page    (56) References JP-A-62-59944 (JP, A)                 JP-A-61-132945 (JP, A)                 JP-A-60-162244 (JP, A)                 JP-A-1-92737 (JP, A)                 JP 62-223752 (JP, A)                 JP 63-116146 (JP, A)                 JP 63-173040 (JP, A)                 JP 63-221341 (JP, A)

Claims (1)

(57) [Claims] At least one side of the support has a photosensitive silver halide emulsion layer containing two or more kinds of surface latent image type silver halide emulsions having substantially different photographic characteristics, and the two or more kinds of silver halides. At least one monodisperse emulsion of the emulsion, a sensitizing dye is added to the photosensitive silver halide emulsion layer, and a hydrophilic colloid layer containing the photosensitive silver halide emulsion layer is provided on the side having A silver halide photographic light-sensitive material, characterized in that the amount of gelatin is 2.00 to 3.50 g / m ² . Here, the monodispersity is the following coefficient of variation VC relating to the particle size.
Is 0.20 or less. However, S is the standard deviation, Given by Is the average particle size, ri is the i-th particle size, and ni is the number of particles. 2. The silver halide photographic light-sensitive material according to claim 1, which is processed by an automatic processor having a total processing time of 20 seconds or more and less than 60 seconds.