JPH02273732A - Silver halide photographic sensitive material housed in cartridge - Google Patents

Abstract

PURPOSE:To obviate the degradation in image quality at the time of printing and to reduce the cost per frame by housing the photosensitive material which has a specific photosensitive silver halide emulsion layer into a specific cartridge. CONSTITUTION:The iodine content of the outermost shell of the negative type silver halide particles incorporated into the photosensitive silver halide emulsion layer is <=10mol%. The high-iodine content shell contg. the iodine at the ratio higher by >=6mol% than in the outermost shell is provided. The silver halide emulsion in which the iodine content in the intermediate shell is higher by >=3mol% than in the outermost shell and the iodine content of the high-iodine content shell is higher than >=3mol% than in the intermediate shell is incorporated into the above-mentioned layer. The effective image plane area per frame to be exposed to the photosensitive material in the aperture is 3.0 to 25.0cm<2> and the ratio of the length on the long side to the length on the short side of the image plane of one frame is 1.2 to 2.0. The degradation in the image quality at the time of the printing is obviated in this way and the cost per frame is reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material housed in a cartridge.

(Prior Art) Conventional cartridges for silver halide photographic materials have a screen size of 2.8 cr! LX 2.85cIIL
The so-called instamatic size 126 size cartridge (standard content is ANSI/ASCPH1,4O-
1984) and the so-called pocket size 110 size cartridge (1.3m x 1.7cIn) (ANSI/A
SCPH1, 55-1986), etc. have been used.

It is true that these cartridges have advantages such as being easy to load into the camera, preventing malfunctions, eliminating the need to wind the film when taking it out after shooting, and making it easy to take out and reload the film during shooting. However, the usage rate has been decreasing recently due to small screen sizes (poor image quality when printed, print aspect ratio close to 1.0, hard to see prints, etc.).

In addition, disposable photosensitive material cartridges such as Utrun-de and Ut-Run-de Hu have recently become popular, but because they are disposable, they have the problem of being expensive per frame. there were. Therefore, there has been a need for a photosensitive material for cartridges that is easy to handle, has high image quality, and is inexpensive.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a photosensitive material housed in a cartridge that does not deteriorate the image quality during printing, and secondly, the camera is not disposable and can be used for each frame. The purpose of the present invention is to supply the photosensitive material at a low price.

(Means for Solving Problem #!1) These objects of the present invention have been achieved by the following color photographic material.

In a silver halide photographic light-sensitive material housed in a cartridge, a light-sensitive silver halide emulsion layer of the light-sensitive material has an inner core substantially consisting of silver bromide and/or silver iodobromide; Negative-working silver halide grains are provided outside the inner core and have an outer shell consisting essentially of silver bromide and/or silver iodobromide. An iodine-rich shell whose outer shell has an iodine content of 10 molts or less and whose iodine content is 6 molts or more higher than the outermost shell is provided inside the outermost shell, and the outermost shell and the iodine-rich shell An intermediate shell having an iodine content between these two shells is provided between the shell and the iodine-rich shell, and the iodine content of the intermediate shell is 3 molt or more higher than that of the outermost shell, and the iodine content of the high iodine-containing shell is A film roll chamber containing a silver halide emulsion whose content is 3 or more moles higher than that of the intermediate shell, and in which the cartridge stores a roll of unexposed photosensitive material, a winding chamber for winding up the exposed photosensitive material, and the like; and a bridge portion having an opening, and furthermore, the effective screen area per frame exposed to the photosensitive material at the opening is 3.0 cIrL2 or more25
．． 0crfL2 or less, and the ratio of the length of the long side to the length of the short side of the screen of one frame is 1.2 or more and 2.0 or less)) Halogenated tank stored in IJ Tsuji Momshin photosensitive material.

The cartridge of the present invention comprises a film roll chamber for storing a roll of unexposed photosensitive material, a take-up chamber for winding up the exposed photosensitive material, and a bridge section connecting them and having an opening. Effective screen area per frame exposed to photosensitive material is 3.0cIrL
25.0 cm or less, and the ratio of the length of the long side to the length of the short side of one frame of screen (aspect ratio) is 1.2 or more and 2.0 or less.

The preferred effective screen area is 6.0 cm or more 16.0 cm
12 or less, particularly preferably 8.0 cIrL2 or more and 10.0 crn2 or less. If the effective screen area is too small, image quality such as graininess and sharpness will not be acceptable to general users. If the effective screen area is too large, the size of the camera will become large and general users will not be able to easily enjoy taking photos anytime and anywhere.

A preferred aspect ratio is 13 or more and 1.7 or less.

Generally, the preferred aspect ratio is said to be the golden section (1,6), but the optimal aspect ratio for photographic prints was determined based on monitor results for general users.

In particular, the service system for the current 135 format color negative/benocou love system is very complete, and it is highly desirable for the user to select a screen size and film width that are compatible with the system.

The preferred film width is 35±1 m/m, preferably 35±0.5 m/m.

Figure 2 shows the appearance of a typical car) IJ Tsuji.

Further, FIG. 1 shows a conceptual diagram of the relationship between the cartridge and the camera immediately before it is inserted into the camera. Traditional this evening.

It was common knowledge that light-shielding paper was used in Eve cartridges, as disclosed in Japanese Patent Publications No. 39-14406 and (H440-17829). However, the presence of light-shielding paper meant that the This is not desirable because it causes deterioration in the flatness of the film, making it difficult to obtain sharply focused photographs, and increasing the screen size (which reduces the effect by half).Therefore, it is recommended to remove the light-shielding paper and adopt another light-shielding method. Preferred. Specific examples of the light shielding means are illustrated below.

(Attach a ribbon like the one used at the outlet of the 11135 cartridge to the exit of the film roll chamber and the entrance of the take-up chamber. The preferred ribbon width is f'iIO ± 5 m/m. The preferred height of the IJ &n is 1.5±0゜3 m
/ m.

(2) Utility Model Publication No. 46-30055, JP-A-54-1
Light-shielding passages, such as those disclosed in Japanese Patent No. 11822, are provided at the exit of the film roll chamber and the entrance of the winding chamber. The light-shielding passage is located at 1/1 of the outer circumference of the roll chamber and winding chamber.
Preferably, the length is 8 or more.

(3) Provide a reson bag as disclosed in Japanese Patent Application Laid-Open No. 58-147742.

(4) Dye the film base with dye to reduce light 9 ipping. There are no particular limitations on the dye, but due to the general properties of photosensitive materials, it is preferable to dye the dye with a color tone close to gray. The staining density is small (both 0.01 or more, preferably 0.03 or more). Measurement is carried out in the visible light range using a color density liver manufactured by Macbeth.

(5) Heat deformation in the form of twill knurling is applied to the leading and trailing ends of the film to reduce light piping.

It is preferable to apply thermal deformation in the form of twill knurling over a distance of 20 m/m or more.

(Means 11 to (5) may be appropriately combined or used alone. (1) and (3), (1) and (4), (
1) and (5), (2) and (3), (2) and (4), (2
) and (5) are preferred.

In order to maximize the effect of increasing the screen size, K creates a reference plane on the camera and cartridge so that the film surface is at a certain level with respect to the lens in the camera. It is preferable that the position of the film surface with respect to the lens is determined by contact.It is preferable to ensure a positional accuracy of ±50 μm.The position of the film surface is determined by pressing the back of the film in the exposed part of the cartridge with the pressure plate of the camera. You can also decide.

The cartridge used in the present invention is usually formed from a plastic material, and the cartridge body is preferably hermetically packaged in a moisture-proof sealed container (cartridge case). Further, the cartridge is preferably formed from a plastic material that does not substantially change the photographic performance of the silver halide photographic material even when stored at 60° C. in the cartridge case. Such plastic materials can be selected in the following manner.

A 100I plastic chip of several m/m is placed in a sealed metal container of about 6000 cIIL moistened with 70% Ky4 glycerin and a film to be packaged with anti-3 protection.
Heat at 0°C for 3 days. Films tested under the same conditions as above, except without the plastic chip, are processed at the same time. The processed film is measured at Status M density, and if the difference between the cyan, magenta, and yellow capri densities of two samples is within 0.10, preferably within 0.005, it can be preferably used as the plastic material of the present invention.

The development process is 3D, which is the standard specification for each color film.
K Therefore, implement it.

For example, in the case of color negative film, C-41, CN
Use -16 etc. For color reversal film, use 0R-56, E-6, etc.

Furthermore, in the present invention, the above plastic material is
It is preferable that the amount of cyan gas generated is 0.03 μI/i or less.

As a result of detailed analysis of the gas components emitted from plastic materials that are harmful to color films, a trace amount of cyan gas was detected.According to the analysis results, the film was placed in a sealed container made of a dialkaline earth metal with a trace amount of cyan gas instead of plastic.
Heating for 3 days at 0.degree. C. showed changes in photographic performance that were very similar to those tested with plastic materials.

These experiments show that plastic materials that do not generate cyan gas are highly preferred for the present invention.

The plastic material preferably used in the present invention has a cyan gas amount of 0.03 μy or less relative to the plastic material ly, and preferably has a cyan gas amount analyzed by the cyan gas detection and quantitative method described below.

It is a plastic material with a detection limit of (0,005 μ9/11) or less.

(Cyan gas analysis method) If necessary, the resin is solidified by cooling with liquid nitrogen, crushed, and used as a sample. This sample was tested in accordance with 38 of JIS K 0102 Factory Wastewater Test Method. Among the sections on cyanide, 38, 1.1.
1. Treat the sample in a manner similar to the aeration method, and collect the generated hydrogen cyanide in a sodium hydroxide solution. The cyanide ions in this collection liquid are determined by the above-mentioned test method 38.2 pyridine-pyrazolone absorptiometric method.

An example of actual analysis is described below.

Take 100 g of resin, add 100 g of water, adjust the voice to 5.0 with acetic acid and sodium hydroxide, keep a constant temperature water bath at 60 ° C, and ventilate at a rate of about 1.2 t/min for 24 hours. Hydrogen cyanide is generated and absorbed into IN-sodium hydroxide solution. The absorbance of this absorption liquid at 620 nm was read using the pyridine-pyrazolone spectrophotometry method, and the absorbance obtained in the blank operation was subtracted (. Using a separately prepared calibration curve, determine the amount of hydrogen cyanide generated, and calculate the amount per 1 g of sample. Calculate the amount of generation.

The plastic material used in the present invention includes addition polymerization of olefins having carbon-carbon double bonds, ring-opening polymerization of small-membered ring compounds, and polycondensation (condensation polymerization) between polyfunctional compounds of 2aI or more.
It can be produced using methods such as , polyaddition, and addition condensation of a phenol derivative, urea derivative, or melamine derivative with a compound having an aldehyde.

The raw materials for glasstics materials include olefins with carbon-carbon double bonds, such as styrene, α-methylstyrene, butadiene, methyl methacrylate, butyl acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N- Typical examples include vinylcarbazole, N-vinylpyrrolidone, vinylidene cyanide, ethylene, and propylene. In addition, examples of small ring compounds include ethylene oxide, propylene oxide, glycidol, 3,3-bischloromethyloxetane, 1,4-soxane, tetrahydrofuran, trioxane, ε-caglolactam, β-propiolactone, ethyleneimine, tetra Typical examples include methylsiloxane.

Further, as polyfunctional compounds, for example, carboxylic acids such as terephthalic acid, adipic acid, and glutaric acid, incyanates such as toluene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, alcohols such as ethylene glycol, propylene glycol, and glycerin, Typical examples include amines such as hexamethylene diamine, tetramethylene diamine, and para-phenylene diamine, and epoxies. Further, typical examples of phenol derivatives, urea derivatives, and melamine derivatives include phenol, cresol, methoxyphenol, chlorophenol, urea, and melamine. Furthermore, compounds with aldehydes include formaldehyde, acetaldehyde,
Typical examples include octanal, dodecanal, and benzaldehyde. Not only one type but also two or more types of these raw materials may be used depending on the target performance.

When producing plastic materials using these raw materials, catalysts and solvents may be used.

As a catalyst, (]-phenylethyl)azodiphenylmethane, dimethyl 2,2'-azobisisobutyrate,
2. Radical polymerization catalysts such as 2'-azobis(2-methylpropane), benzoyl peroxide, cyclohexanone peroxide, potassium persulfate, sulfuric acid, toluenesulfonic acid, trifluoro-sulfuric acid, perchloric acid, trifluoroboron, Cationic polymerization catalysts such as tin tetrachloride, n-
Anionic polymerization catalysts such as butyllithium, sodium/naphthalene, 9-fluorenyllithium, phenylmagnesium bromide, triethylaluminum/tetrachlorotitanium-based Ziegler-Natsuta
-Vatta) type catalyst, sodium hydroxide, potassium hydroxide, potassium metal, etc. are used.

There are no particular restrictions on the solvent as long as it does not inhibit polymerization, but examples include hexane, decalin, benzene, toluene, cyclohexane, chloroform, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, and tetrahydrofuran.

In molding the plastics of the present invention, a plasticizer is mixed with the plastics as necessary. Examples of the plasticizer include trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sepacate, methyl amyl ketone, nitrobenzene, γ-valerolactone,
Representative examples include di-n-octyl succinate, bromonaphthalene, and butyl palmitate.

Specific examples of plastic materials used in the present invention are listed below, but are not limited to these (1° polystyrene polyethylene polypropylene polymonochlorotrifluoroethylene vinylidene chloride resin vinyl chloride resin vinyl chloride-vinyl acetate copolymer resin acrylonitrile -Butadiene-su P-1 1 P-1 2 P-1 3 P-1 4 Thyrene copolymer resin Methyl methacrylic resin Vinyl formal resin Vinyl butyral resin Polyethylene phthalate Teflon Nicene P-15 Phenol resin P-16 Melamine resin book Particularly preferred plastic materials for the invention are polystyrene, polyethylene, polypropylene, and the like.

Cartridges are usually manufactured using plastic mixed with carden black or pigments to give them a shimmering effect.

The total weight of the cartridge is usually 5 to 70 g, preferably 10 to 50 g, more preferably 12 to 30 g.

In the present invention, it is preferable that the cartridge be packaged in a sealed state inside a cartridge case, and here, airtight packaging means that the inside of the case after 12 months at 25°C, assuming a 20% humidity difference between the outside air and the inside of the case A state in which the change in if is within 10%.

As the cartridge case, a plastic case such as a 135 size cartridge case or a moisture-proof bag such as a 110 size or 120 size film case can be used.

The humidity inside the cartridge case is usually 45 to 70 degrees relative humidity at 25 DEG C., preferably 50 to 851 degrees Celsius, more preferably 52 to 601 degrees Celsius.

Cellulose triacetate, polyester paste, etc. can be used as the film base. When using a polyester paste, it is preferable to use a water-absorbing polyester base as described in Japanese Patent Application No. 71308/1983.

The thickness of the film base is usually 40 to 140 μm, preferably 60 to 130 μm, more preferably 80 to 1
It is 20 μm.

In the silver halide composition of the silver halide grains according to the present invention, the above-mentioned "J consisting essentially of..." means silver bromide or silver iodobromide to the extent that it does not impair the effects of the present invention. This means that it may contain silver halides other than the above, such as silver chloride, and specifically, in the case of silver chloride, the ratio #
It is desirable that it be less than i1 molti.

To summarize the features of the photographic material according to the present invention,
As shown in (1) to (8) below.

(1) By using an emulsion containing core/shell type nolognized silver grains with a high iodine shell on the inside (compared to a non-core/shell emulsion), high sensitivity, wide exposure range, and excellent graininess can be obtained. .

(2) Between the high iodine shell and the surface low iodine shell (outermost shell #),
Even higher sensitivity can be obtained by providing an intermediate shell having an intermediate iodine content.

(3) The iodine content of the high iodine shell is preferably 6 to 40 moltches (6 molts or more than the outermost shell layer). If it is less than 40 molts, the sensitivity will decrease, and if it exceeds 40 molts, it will become polydisperse, so from the viewpoint of sensitivity and sharpness, it is preferable not to exceed 40 molts.

(4) The difference in iodine content between the middle shell and the outermost shell or high iodine shell should be at least 3 molt.
If this difference is too small, the effect of the intermediate shell will be small (sensitivity will decrease).

Further, it is desirable that the upper limit of this difference in iodine content is 35 molty from the viewpoint of effectively bringing out the effects of the intermediate shell (sensitivity, monodispersity, Capri-sensitivity relationship, sharpness).

(5) If the iodine content in the entire silver halide grain is too high, developability will be poor and sensitivity will be lowered; if it is too low, the gradation will be too hard, the exposure range will be narrow (or grainy). Therefore, it is preferable to select a specific range.

(6) A monodisperse emulsion is superior to a polydisperse emulsion in terms of sensitivity, sharpness, and Capri-sensitivity relationship. That is, in polydispersion, the shell-forming reaction is non-uniform, making it difficult to form an ideal core/shell structure, the presence of small particles that degrade sharpness, and chemical sensitization after particle formation. Since the optimum conditions differ depending on the individual grains, the sensitivity tends to be low and the Capri-sensitivity relationship tends to deteriorate, so monodisperse emulsions are preferably used.

(7) In multilayer color light-sensitive materials, the development of multiple layers causes deterioration in sensitivity compared to the case of a single layer (referred to as multilayer desensitization effect). Not only is it expensive, but it is also less susceptible to this multilayer desensitization effect and can be used more effectively in multilayer color photosensitive materials.

In order to further improve the above-mentioned excellent effects, Ih: Iodine content of high iodine shell (molti) 1m: Iodine content of intermediate shell (mol%) T: Iodine content of outermost shell (mol%) ), ΔI=Ih-1t)8molti, ΔIh=I
h-Im) 4 molts, Δrt=Im-t:) 4 molts, ΔI>10 molts, ΔIh) 4 molts, ΔIt) 4 molts (above (4))
).

Here, it is preferable that It=0 to 5 moles, preferably 0 to 2 moles, and more preferably θ to 1 mole. Also,
Ih is preferably 6 to 40 molar, and even more preferably 10 to 40 molar ((3) above).

In addition, the volume of the outermost shell is 4 to 70 molti of the entire particle (
, 10 to 50 molti is more preferable. The volume of the high iodine shell is preferably 10 to 80% of the whole grain, and 20% to 80% of the whole grain.
~50%, more preferably 20 to 45 inches. The volume of the intermediate shell is preferably 5 to 60%, more preferably 20 to 55%, of the entire particle. The high iodine shell may be a small part of the inner shell, but preferably an internal core is present inside the high iodine shell.

The iodine content of the inner core is 0 to 40 molt (,0 to 10
Morti is preferred, and 0 to 6 morti is more preferred. The particle size of the inner core is 0.05 to 0.8 μm, and even 0.05 to 0.
．． 4 μm is good.

In addition, regarding the characteristic point (5) above, the iodine content Vi in the entire particle is preferably 1 to 20 molt, preferably 1 to 20 molt.
It is desirable that the amount is 15 molti, more preferably 2 to 12 molti. Regarding the characteristic point (6) above, the particle size distribution of the particles may be either polydisperse or monodisperse, but it is preferable that the coefficient of variation of the particle size distribution be a monodisperse emulsion of 20% or less; It is preferable that the coefficient of variation be 15% or less. This coefficient of variation is defined as , and is a measure of monodispersity.

The grain size of the halogenated steel grains (defined as the length of one side of a cube with the same volume as the silver halide grains) is 0.1 to 3.0.
It is preferable to set it to μm. Moreover, the shape may be any of an octahedron, a cube, a sphere, a flat plate, etc., but an octahedron is preferable.

To further describe the layer structure of the silver halide grains of the present invention, the internal core and the high iodine shell may be the same as described above, or the internal core may be provided separately inside the high iodine shell. Also good. The inner core and the high iodine shell, the high iodine shell and the middle shell, and the middle shell and the outermost shell may each be adjacent to each other, or at least is another shell having an arbitrary composition between each shell. (This is called an arbitrary shell).

These arbitrary shells may be a single shell with a uniform composition, a group of shells consisting of multiple shells with a uniform composition whose composition changes stepwise, or continuous shells within an arbitrary shell. It may be a continuous film whose composition changes, or it may be a combination of these. Further, there may be a plurality of high-iodity shells and intermediate shells, or there may be only one set.

Next, an example of the 7111 configuration of the halogenated steel particles according to the present invention will be explained. Iodine content is expressed in units.

1. Inner core = three-layer structure of high iodine shell Iodine content shell diameter core (third) (inner core = 1.-I2) 3 mol% I,
= 15 mo A41.2 μm high iodine shell) 2nd shell (intermediate shell) I2-r, ) 384b I2-58
% 1.4μrn 1st shell (outermost shell) r, =
0-1 m I , = 05 so 41.6 μm2, six-layer structure including fourth and fifth shells of arbitrary composition between the inner core and high iodine shell Shell diameter core (sixth) (internal Nucleus) Any X6=4D-TJvyb
O11μm 5th shell (-) optional l5=2j)-EJvl
b027μm 4th shell (-) optional 1a=2trEJL'
lb OBttm 3rd shell■wo Jfllk)I3-I2)
3%4 I, = 15. Omo L41.12/jm 2nd
Shell (intermediate shell) I2-I, >3%/L4 l2=5.0
MoL96 1.44μm 1st shell (outermost shell) I, =
0~1m I, = 0.5%A4 1.6ttm3, any 5th and 6th shells between the inner shell and the high iodine shell, and the middle of the two layers between the outermost shell and the high iodine shell 7F with shell @ structure Iodine content shell diameter 4th shell (high iodine shell H4-13) 3 mo'% I a = 15
``'461.12μm 4th shell (optional shell) Arbitrary!
=9Mo rod 1.24μm 3rd shell (intermediate shell) I, -I, =
3% A$ I 3 = 5 mo M4 1.44 μm 2nd shell (arbitrary shell) Arbitrary l2 = 4.57 41.50 μm 1st shell (outermost shell) 11 = () - 10% 1L4I, = 2 moles %
1.6μm5, structural iodine content with multiple high iodine shells Shell diameter 6th shell (inner core) Arbitrary I b; 474o, 10
1 layer m 1st shell (# outer shell) I, = f) -10-T4
I, =O-')MoL41.6μm4, any 6th and 7th shells between the inner shell and the high iodine shell, and the high iodine shell (5th shell) and the intermediate shell (3rd shell). 5b with one layer of arbitrary shell (fourth shell) in between, and one layer of arbitrary shell (second shell) between the intermediate shell (third shell) and the outermost shell ) Arbitrary !8=4-EJL4!I 7th shell (arbitrary shell) Arbitrary ■7=2Mo 6th shell (arbitrary shell) Arbitrary Engineering, = 4Mo 4 5th shell (high iodine shell) I
5-I3>34A4 l5=15mo→shell diameter 0.10μm 0.27μm 0.8μm 1.12μm 4th shell (optional shell) Arbitrary I 4 =5%A4 0
．． 80 /Am 2nd shell (intermediate shell) I2-I, ) 3 mo
■2 = 5 Seven Yu 1.44μm 1st shell (outermost shell) I, =
10%/14 I, = 0.3% A4 1.60 μm The inner core of the silver halide grain of the present invention is described by Chimie at Physiqu by Glafkides, P.
e.

Photohraphique (published by pau1Mont@l, 1967), written by G. F. Duffin
Photographic I°Mulsion Kepostri (Ph
otographic Iiknulsion Chlm
istry) (The Focal Press (TheFo
cal Pr@ms), 1966), Gui L.
Making and Coat Photographic Imulsion by Zelikman (V, L, Ze 1 Ikman) et al.
ing Photographic Emulsion)
(The Focal Press
It can be prepared using the method described in (Res.), 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which PAlr in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Although two or more silver halide emulsions formed separately may be used as a mixture, it is preferable to use the double jet method or the controlled double jet method.

The PAg used when preparing the inner core varies depending on the reaction temperature and the type of silver halide solvent, but is preferably 2 to 11. Further, it is preferable to use a silver halide solvent because the grain formation time can be shortened. For example, commonly known silver halide solvents such as ammonia and thioether can be used.

The shape of the internal core may be plate-shaped, spherical, twinned, or octahedral, cubic, tetradecahedral, or mixed.

Also, to make the particle size uniform, British patent 1.53
No. 5,016, Special Publication No. 48-36890, No. 52-16
As described in No. 364, silver nitrate and ha can be prepared by changing the addition rate of an aqueous alkali gunide solution according to the particle growth rate, and in U.S. Pat. As described above, it is preferable to use a method of varying the aqueous solution concentration to grow quickly within a range that does not exceed the critical saturation level. These methods do not cause renucleation and each silver halide grain is uniformly covered, so they are preferably used when introducing arbitrary shells, high iodine shells, intermediate shells, and outermost shells. .

If necessary, a single shell or a plurality of arbitrary shells may be provided between the high iodine shell and the inner shell of the silver halide grains of the present invention. This high iodine shell is formed by a conventional halogen substitution method, a silver halide coating method, etc. after a desalination process is applied to the formed inner core or the inner shell to which an optional shell has been added, if necessary. be able to.

The halogen substitution method can be carried out, for example, by adding an aqueous solution mainly consisting of an iodo-9 compound (preferably potassium iodo), preferably at a concentration of 10% or less, after the internal core is formed. Permit, U.S. Pat. No. 2,592.250, No. 4,
This can be carried out by the methods described in Meiwaisho No. 075,020, JP-A-55-127549, and the like. At this time, in order to reduce the difference in iodine distribution between particles in the high iodine shell, it is desirable to reduce the concentration of the iodine compound aqueous solution to 10 molar or less and add it over 10 minutes. The new coating with silver oxide can be carried out, for example, by simultaneously adding an aqueous halide solution and an aqueous silver nitrate solution, that is, by a simultaneous mixing method or a controlled double jet method. For details, see Japanese Patent Application Laid-open No. 53-22408, Japanese Patent Publication No. 43-1
No. 3162, Japanese Unexamined Patent Publication No. 14829/1983, J Photo Science (J, Photo, Sei
, ), 24, 198 (1976).

pAg when forming a high iodine shell is the reaction temperature,
Although it varies depending on the type and amount of the silver halide solvent, those mentioned above are preferably used. When using ammonia as a solvent, the amount is preferably 7 to 11 liters.

As a method for forming a high iodine shell, a simultaneous mixing method or a controlled double jet method is more preferable.

The intermediate shell of the silver halide grains of the present invention includes a high-iodide shell having a high-iodide shell on the surface, or a high-iodide shell having a single or plural arbitrary shells on the high-iodide shell as necessary, and an inner core. It is possible to provide silver halide having a halogen composition different from that of the outer grains containing alK1 and the high iodine shell by a simultaneous mixing method or a controlled double jet method.

Regarding these methods, the method of providing a high iodine shell described above is similarly used.

The outermost shell of the silver halide grains of the present invention includes an intermediate shell, a high iodine shell, and an inner shell having an intermediate shell on the surface or having a single or plural arbitrary shells on the intermediate shell as necessary. On the outside of the particle containing J! Silver halide having a halogen composition different from that of the high iodine shell can be coated on the surface by a simultaneous mixing method or a controlled dog pull-jet method.

Regarding these methods, the above-mentioned method of providing a high iodine shell is similarly used.

One or more optional shells can be provided between the inner shell and the high iodine shell, between the high iodine shell and the intermediate shell, and between the middle shell and the outermost shell, or there is no need to provide one. good. For these arbitrary shells, the above-mentioned method for providing high iodine shells can be similarly used. In the inner shell, high iodine shell, intermediate shell, outermost shell, and any shell in each F, a desalination step may be carried out according to a conventional method as necessary during the preparation of adjacent shells, or
The desalination step may be carried out. [The shell formation may be carried out in small successions.

Regarding the iodine content of each shell of the silver halide grains of the present invention, for example, J, 1. Goldstein (Gol)
dateIn), D, B, Willi
-ams) "X-ray Analysis in rTIM/A'lEM" Scanning Electron Microscope (19
77), Volume 1 (IIT Research Institute, page 651 (March 1977)).

The silver halide grains as the final product after the formation of the outermost shell of the present invention are free from excess halogen compounds produced during preparation, by-products or unnecessary salts and compounds such as nitrates and ammonia, as a dispersion medium for the grains. may be removed from

The removal method can be the Tardel water washing method or dialysis method commonly used for general emulsions, or inorganic salts, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. acylated gelatin, carbamoylated gelatin, etc.). ) can be used as appropriate.

The core/shell type silver halide grains of the present invention can be optically sensitized to a desired wavelength range. There are no particular restrictions on the optical sensitization method; for example, optical sensitization can be carried out using cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or optical sensitizers such as merocyanine dyes, either alone or in combination. I can do it. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

Along with sensitizing dyes, dyes that themselves do not have a spectral sensitizing effect or substances that do not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. These techniques are described in U.S. Pat. No. 2,688.545, box 12.
．． No. 912,329, No. 3.397゜060, Ashi 13
．． No. 615,635, No. 3,628.964, British Patent No. 1,195,302, No. 1,242,588, No. 1,293.862, West German Patent (OLS) 2.030
, No. 326, No. 2,121,780, Special Publication No. 43-4
No. 936, No. 44-14030, Research Disclosure (Research Dtacloaur@)
It is also described in vol. 176, 17643 (published December 1978), page 23, item 5, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

The core/shell type silver halide crystals of the present invention can be subjected to any one of the chemical sensitization methods applied to general emulsions.

For chemical sensitization, use a bar freezer (H.

Di@Grand1mgend@r P
photograph1seh@Prozssse ml
t Sllber-halog@nid@n)
miach@Verlsgs-ges*11sehaf
t), 1968), pp. 675-734, can be used. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and their related compounds can be used.
74,944, 2,410.689, 2,278.
No. 947, No. 2,728,668, 3.656°955
No. 4,032,928, and No. 4,067,740. Reduction sensitizers include stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds etc. can be used, and specific examples thereof include U.S. Pat.
No. 2,518,698, 2゜983.609, 2
, 983.610, 2,694,637, 3,93
No. 0,867 and No. 4,054,458. For noble metal sensitization, in addition to gold complexes, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used as K.
No. 2,448,060, British Patent No. 618,061, etc.

For the silver salt particles of the present invention, a combination of two or more of these chemical sensitization methods can be used.

Various dopants can be doped during the formation of each shell of the core/shell emulsion of the present invention. For example, silver, sulfur, iridium,
Gold, platinum, osmium, rhodium, tellurium, selenium, cadmium, zinc, lead, thallium, iron, antimony,
Contains bismuth, arsenic, etc. In order to dope the stiff dopant, water-soluble salts or complex salts of each type can be present at the time of formation.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular restrictions on the number or order of layers and non-photosensitive layers.A typical example is to prepare a plurality of silver halide emulsions with substantially the same color sensitivity but different photosensitivity on a support. A silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of a layer, the light-sensitive layer being a unit light-sensitive layer having sensitivity to any of blue light, green light, and red light; In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in this order from the support side: a red-sensitive layer, a green-sensitive layer, and a front-pane color layer. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20037 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121.470 or British Patent No. 923.045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (Bl() / high-sensitivity green-sensitivity layer (GH) / low-sensitivity green-sensitivity layer ( GL)/
High-sensitivity red-sensitive FJ (RH) / low-sensitivity red-sensitive layer (
RL) or BH/BL/GL/G)I/RH/
RL order or BH/BL/Gll/GL/RL/R
) can be installed in the order of I, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/I
They can also be arranged in the order of ll/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/R1 (blue-sensitive layer/GL/RL/GH/R1) may be arranged in this order from the farthest side from the support. can.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when composed of 3N having different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, the medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-irradiation emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the following order: low-speed emulsion N/medium-speed emulsion layer/high-speed opalescent layer.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) Nα17643
(December 1978), pp. 22-23, '■, Emulsion preparation an
d types)'', and the same seed 18716 (197
(November 9), , 64B pages, "Physics and Chemistry of Photography" by Glafkid, published by Paul Montell (P, Glafkid
es, Chea+ie et Ph1sique P
photograph-fque, Paul Mont
el+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin.

Photographic Emulsion Che
+*tstry (Focal Press.

1966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Zeliks)
anet al,, Making and Coat
ing Photographic E+5ul-si
on+ Focal Press+ 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by GuLoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
．． No. 434,226, No. 4,414.310, No. 4,
433.048, British Patent No. 4,439.520, and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure Nct
17643 and Na 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Attachment 15 1 plate Average H Dwarf L Other month l excluded 1 Chemical sensitizer page 23 Page 648 right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Antifoggant Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorber 7 Anti-stain agent Page 25 right i Page 650 left to right column 8 Dye image stabilizer Page 25 9 Hardener page 26 Page 651 left column lO binder Page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 right column 12 application aid,
Pages 26-27 Page 650 Right column Surfactant 13 Static Page 27 Same as above Patch In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
．． It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503.

Various color couplers can be used in the present invention, and specific examples of the color couplers are described in the above-mentioned Research Disclosure (
RD) Sou 17643, described in the patents listed in ■-CG.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, same No. 4,022,620, same No. 4,
326, 024, 4,401.752, 4.248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1.425,020, 1,476.76
No. 0, U.S. Patent No. 3,973,968, U.S. Patent No. 4.31
Preferred are those described in European Patent No. 4.023, European Patent No. 4.511.649, European Patent No. 249.4738, and the like.

As magenta couplers, 5-pyrazolone and pyrazoloazole thread compounds are preferred, and US Pat.
No. 0.619, No. 4.351.897, European Patent No. 73.636, US Patent No. 3.061,432, US Patent No. 3.725.067, Research Disclosure No. 24220 (June 1984) month), JP-A-60-3
No. 3552, Research Disclosure Na 24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Patent No. 4.500.630, No. 4.540,654
No. 4,556,630, International Publication WO3810
Particularly preferred are those described in No. 4795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052.212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4.296.200, No. 2,369.9
No. 29, No. 2.801.171, No. 2,772.
No. 162, No. 2,895,826, No. 3.772
．． No. 002, No. 3,758,308, No. 4,33
No. 4.011, No. 4,327.173, West German Patent Publication No. 3゜329.729, European Patent No. 121,365
A, No. 249°453A, U.S. Patent No. 3.446
, No. 622, No. 4,333,999, No. 4,77
No. 5,616, No. 4,451,559, No. 4,
427, No. 767, No. 4, 690, 889,
Preferred are those described in JP-A No. 4,254.212, JP-A No. 4,296.199, JP-A-61-42658, and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure Seed 17643.
- Section G, U.S. Patent No. 4.163.670, Special Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138.258, British Patent No. 1,146.
The one described in No. 368 is preferred. In addition, the U.S. patent cylinder 4
, 774,181, which corrects unnecessary absorption of coloring dyes by the fluorescent dye released during coupling; and U.S. Pat. No. 4,777,120, which reacts with a developing agent to form a dye. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, EP 96,570 and DE 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 20, No. 4,576°910, British Patent No. 2.10
2.1'73, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the l? D l764
3. Patents listed in sections ■ to F, Japanese Patent Application Laid-open No. 7-1519
No. 44, No. 57-154234, No. 60-1842.
No. 18, No. 63-37346, U.S. Pat. No. 4,248.
No. 962 and No. 4°782.012 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2,131,188 1. Japanese Patent Publication No. 59-15763
No. 8 and No. 59-170840 are preferred.

In addition, examples of couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , D[R redox compound releasing couplers, DIR coupler releasing couplers, described in JP-A-60-185950, JP-A-62-24252, etc.
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜3
No. 02A, a coupler releasing a dye that after-breaks after coloring, +1.0. 11449, 24241, JP-A-6
Bleach accelerator releasing couplers described in US Pat. No. 1-201247 etc., ligand releasing couplers described in US Pat. Cylinder 4,774.1
Examples include couplers that emit fluorescent dyes as described in No. 81.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Patent No. 2,322.027 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid esters (dibutyl tucrate, dicyclohexyl phthalate, di-2.ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl)). phthalate, bis(2,4, diamyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid Nisdels (triphenyl phosphate, tricresyl phosphate, 2
-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetra decylpyrrolidone, etc.), alcohols or phenols (stearyl alcohol, 2.
4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2
-poxy-5-tert-octylaniline, etc.),
Examples include hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C.
Organic solvents having a temperature above about 160"C or below can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion process, effects, and latex for impregnation can be found in U.S. Pat. etc. are listed.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, lobutyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nα17643 and Nα18716
It is described from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 20 μm or less, and the film swelling rate TI /! is preferably 30 seconds or less, more preferably 20 seconds or less.

The film thickness is 25'C and 55% relative humidity! ji means the film thickness measured under humidity (2 days), and the film swelling rate T17. can be measured according to techniques known in the art. For example, according to Green, A. et al., Photographic Science and Engineering (PhoLogr, Sci, Eng, ) +
It can be measured by using a swellometer (swelling membrane) of the type described in t9@, No. 2, pages 124-129.
r+7g is defined as the time required to reach a film thickness of T1/2, with 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30° C. for 3 minutes and 15 seconds as the saturated film thickness.

The film swelling rate Tl/□ can be adjusted by adding hardening to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic light-sensitive material according to the present invention is described in the above-mentioned RD, pages 28-29 of 17643, and 6 of 18716.
15. Development processing can be carried out by the usual methods described in the left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although amine phenol compounds are also useful as color developing agents, p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred, and two or more of these compounds may be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. agent, aminopolycarboxylic acid, aminopolyphosphonic acid,
Various chelating agents such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1, Representative examples include 1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N tetramethylenephosphonic acid, ethylenediamine di(0-hydroxyphenylacetic acid), and salts thereof. be able to.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. In this black and white developer, known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as -phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone or Can be used in combination.

The ρ11 of these color developing solutions and black and white developing solutions is 9 to 12.
It is common that The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed; It is less than 32 per square meter, and can be reduced to less than 500 d by reducing the bromide ion concentration during nighttime replenishment. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, Capacity of treatment liquid (cab3) The above aperture ratio is preferably 0.1 or less, more preferably o, ooi to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all processes such as bleaching, bleach-fixing, fixing, washing, and stabilization, and it is also possible to reduce the amount of replenishment by using means to suppress the accumulation of bromide ions in the developer. .

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature, high p)I, and a high concentration of color developing agent. .

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, it is possible to use a processing method in which bleaching is followed by bleach-fixing, furthermore, processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. A post-bleaching treatment can also be optionally carried out depending on the purpose. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds, etc. Typical bleaching agents include R complex salts of iron (I), such as ethylenediamine. Use aminopolycarboxylic acids such as tetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid, etc. be able to. Among these, aminopolycarboxylic acid iron(III) if salts, including ethylenediaminetetraacetic acid iron(I[l) complex salt and 1,3-diaminopropanetetraacetic acid iron(Iil) complex salt, are useful for rapid processing and environmental pollution prevention. Preferable from this point of view, iron aminopolycarboxylate (
I[[) complex salts are particularly useful in both bleach and bleach-fix solutions. These iron aminopolycarboxylic acids (
■) The pH of bleach or bleach-fix solutions using complex salts is usually 4.
．． 0 to 8, but lower ρ for faster processing
11 can also be processed.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893.858, German Pat.
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, 53. ．． No. 72623, 53-95
No. 630, No. 53-95631, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
No. 53-28426, Research Disclosure No. Nα17129 <July 1978), etc. Compounds having a mercapto group or a disulfide group;
Thiazolidine derivatives described in JP-A-50-140129; JP-A-45-8506, JP-A-52-20832
No. 53-32735, U.S. Patent No. 3,706.5
Thiourea derivatives described in No. 61; West German Patent No. 1.127
, 715, and the iodide salts described in JP-A-58-16.235;
Polyoxyethylene compounds described in No. 30;
Polyamine compound described in No. 5-8836; other JP-A No. 49-42.434, No. 49-59,644, No. 5
No. 3-94.927, No. 54-35,727, No. 55
Compounds described in No. 26,506 and No. 5, No. 163,940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,8
No. 58, West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 1983
Preferred are the compounds described in US Pat. No. 4,552,830, and also preferred are the compounds described in US Pat. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C to 45'C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring be as strong as possible.A specific method for strengthening the stirring is the treatment on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461. There is a method of colliding liquid jets, a method of increasing the stirring effect using a rotating means as described in JP-A No. 62-183461, and a method of moving the photosensitive material without bringing the emulsion surface into contact with a wiper blade installed in the liquid. Examples include a method in which the stirring effect is further improved by making the emulsion surface turbulent, and a method in which the circulation flow rate of the entire processing liquid is increased. Such agitation enhancement means include bleaching solutions,
Effective in both bleach-fix and fix solutions.
Pj'e.

Improved agitation speeds up the supply of bleach and fixing agents into the emulsion film,
It is thought that this increases the desilvering rate as a result. Also,
The agitation improvement means described above are more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect of the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

The silver halide color photographic light-sensitive material of the present invention preferably undergoes a water washing and/or stabilization process after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent, forward flow, etc.
It can be set in a wide range depending on various other conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is based on the Journal of the 5ociety
f Motion Picture and Te1e
-vision Engineers Volume 64, P.
248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A-62-28L838 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, and chlorinated sodium incyanurate described in JP-A No. 57-8.542, and other benzotriazoles are also available, as described in Hiroshi Horiguchi's Chemistry of Antifungal Agents. J (1986) Sankyo Publishing, Sanitary Technology Association Ur.
Microbial sterilization, sterilization, and anti-mildew technology J (1982) Industrial Technology Center, Japanese Society of Anti-bacterial and Anti-fungal Agents Encyclopedia of Anti-bacterial and Anti-fungal Agents (1)
It is also possible to use the fungicides described in 1986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

When each of the processing solutions described above undergoes shrinkage due to evaporation during processing using an automatic processor or the like, it is preferable to add water to correct the shrinkage.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3.342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
No. and Is of the same, Schiff base-type compounds described in No. 159,
Aldol compounds described in U.S. Patent No. 13,924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 135628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

In addition, West German Patent No. 2.226.7 was issued for the purpose of saving light-sensitive materials.
70 or US Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.660^2, etc.

Examples will be described below, but the present invention is not limited to these examples.

(Example) According to the method described in JP-A No. 61-250645, N
An emulsion showing -IK was prepared. Each emulsion was chemically sensitized with gold and sulfur and/or selenium sensitizers.

K on a subbed-coated tri-acid cellulose film support;
Each layer having the composition shown below was coated in a multilayer manner to prepare a sample as a multilayer color photosensitive material.

(Photosensitive layer composition) The number corresponding to each component is 1. ! ? The coating weight is expressed in units of /m', and for silver halide, the coating weight is expressed in terms of silver. However, for sensitizing dyes, use halogenated scissors in the same layer! The coating amount is expressed in moles.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 Second layer (intermediate layer) 2.5-di-t-pentadecyl 018 Hydroquinone EX-10, 07 EX-30, 02 EX-120,002 U-10,06 U-20,08 0-30,10 HBS-10,10 HBS-20,02 Gelatin 1.04 3rd NI (1st red-sensitive emulsion NI) Circle equivalent diameter 0. 60 μm 1 AgBrI with a coefficient of variation of 33%,
. Tabular grains (aspect ratio 62)
Silver 0.50 Sensitizing dye 1 6
．． 9X10-5 sensitizing dye 1! 1.
8X10-5 sensitizing dye nl 3. l
X10-'EX-20,335 EX-100,020 U-10,07 U-20,05 U-30,07 HBS-10,060 Gelatin 0.87HBS-10
, 22 HBS-2 Gelatin No. 6 @ (middle #) EX-5 HBS-1 Gelatin No. 7 m (first green-sensitive emulsion layer) AgBr1 with equivalent circle diameter 0.50 μm and coefficient of variation 7.0%
．． Cubic crane sensitizing dye with chipped corners V Sensitizing dye■ Sensitizing dye■ EX-6 EX-1 EX-7 EX-8 B5-1 B5-3 Gelatin No. 8 (second green emulsion layer) 0. 10 1.63 0.040 0.020 0.80 Silver 0.30 3, OX 10"" 1, OX 10-4 3.8 X 10-' 0.260 0.021 0.030 0.025 0. 100 0.010 0.63 AgBrI with equivalent circle diameter 0.60 μm 1 coefficient of variation 7.4
4.0, octahedron with missing corners.

Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-8 EX-7 HBS -1 B5-3 Gelatin No. 9 NI (third green emulsion layer) Emulsion-2 Sensitizing dye V Sensitizing dye ■ Enhancement Sensitive dye ■ EX-13 EX-11 EX-1 B5-1 Silver 0.45 2, lXl0'''5 7, OX 10-5 2.6 X l O-' 0.094 0.018 0.026 0. 160 o, oos O050 Silver 1,2 3.5 Sensitizing emulsion layer) AgB r I 6.0 tabular grains with equivalent circle diameter 1.23 μm and coefficient of variation 16.3% (aspect ratio 7.6) Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ EX-2 EX -3 EX-10 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion-1 Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-3 Silver 1,0 5, lX10'''5 1.4 X 10 '-5 2,3X 10" 0.400 0.050 0.015 0.07 0.07 1.30 Silver 1.60 5.4 X 10-5 1.4 X 10-5 2.4X10-' 0 .010 EX-4 EX-2 B5-2 Gelatin 10th layer (yellow filter layer yellow colloidal silver EX-5 HBS-1 Gelatin 11th layer (first blue-sensitive emulsion NI) Equivalent circle diameter 0.43 μm, coefficient of variation 6 .2% AgBrI
υ, octahedron with following corners.

AgBrI with equivalent circle diameter 0.80 μm and coefficient of variation 8.7
ao - A tetradecahedron with missing corners.

Sensitizing dye■ EX-9 EX-8 EBB-1 gelatin No. 111 (second blue-sensitive emulsion layer) o,os.

O,097 0,10 1,54 silver 0.05 0.08 0.03 0.95 Silver 0.07 silver 0.07 3.5 x 10-' 0.721 0.042 0.28 1.10 Equivalent circle diameter 1.4 μm, coefficient of variation 18.2% AgBrI&o% shaped particles (aspect ratio 6.9) Silver sensitizing dye■ EX-9 EX-10 B5-1 gelatin 13th III (third blue-sensitive emulsion layer) Emulsion-3 Sensitizing dye■ EX-9 HBS-1 gelatin 14th layer (first protection 711) Equivalent circle diameter 0.07 μm 1 coefficient of variation 15 AgB r I 1. , spherical particles.

EBB-1 Silver 0.45 2, I X 10-4 0.154 0.007 0.05 0.78 0.77 2.2 .11 O,17 0.05 Gelatin 1.00 No. 15M
1 (Second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0.548
-1 0.20 Gelatin 1.20 In addition to the above ingredients, 1 gelatin hardening agent H-1 and a surfactant were added to each layer.

Sample 101 and Sample 102 were prepared using emulsions having E m -1+ 2 and 3 shown in Table IK.

The contents are shown in Table-2.

Table-2 EX-1 l EX-2 0I+ EX-3 I’ll ( The structural formulas of each component described in the examples are shown below.

EX-4 EX-5 CbHI 2 (n) EX-6 EX-10 I EX-12 C,)I.

C,H.

CZH, OSOρ EX-7 EX-8 EX-9 EX-13 l I U-4 Sensitizing dye■ Sensitizing dye ■ B5-2 Di-n-butyl phthalate sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Samples 201 to 201, which are multilayer color photosensitive materials stored in cartridges, using Samples 101 and 102 206 was created.

(Creation of Samples 201 and 202) Sample 101 was processed into a 110 cartridge by taking 12 images according to the ANS I standard, left for 2 days at 25°C and 55% relative humidity, and processed under the same conditions with 105t105t Dragon's moisture-proof film (Fuji Film Sample 201 was obtained by sealing the 110 cartridge packaging film and the same film.

Sample 102 was processed into sample 202 in the same manner.

(Creation of Samples 203 and 204) Sample 101 was processed into a 126 cartridge by taking 12 images according to the ANSI standard, left at 25°C and relative humidity of 55% for 2 days, and sealed in a 106n x 50n moisture-proof film (same as above) under the same conditions. The sealed sample was designated as sample 203.

Sample 102 was processed into sample 204 in the same manner.

(Preparation of samples 205 and 206) Place sample 101 in a car as shown in Figure 2)
Sample 205 was obtained by processing two images, diffusing them at 25° C. and relative humidity of 55° C. for 2 days, and sealing them in a 120 ym×60 tm moisture-proof film (Eup 1 upper) under − conditions. The screen size of this cartridge is 24m x 36m.

Sample 102 was processed into sample 206 in the same manner.

Samples 201 to 206 were loaded into a camera, and practical evaluations of people and scenery were performed. Evaluation was performed on print samples.

The camera used is Minolta Zoom SLR mark for the 110 cartridge, and KOD A KIN ST AMATIC for the 126 cartridge.
500, the cartridge of the present invention was a Fuji Tough Guide camera that had been modified by removing the back cover, etc., and the zoom or distance was adjusted to make the size of the subject the same.

The exposed film thus obtained was processed using an automatic processor in the manner described below (until the cumulative replenishment amount of the bleaching solution was three times the volume of the mother liquor tank).

Processing method step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38℃ 3317 20
L bleach 6 minutes 30 seconds 38℃ 251/
4OL water washing 2 minutes 10 seconds 24℃ 1200iu
20L fixation 4 minutes 20 seconds 38℃ 25 seconds 30L water washing (1) 1 minute 05 seconds 24℃ (IOL countercurrent piping system from 2 to (1).

Water washing (2) 1 minute 00 seconds 24℃ 1200mj
IOL stability 1 minute 05 seconds 38℃ 251R
IIOL drying 4 minutes 20 seconds 55°C Replenishment amount is 35°C width In length Next, write down the composition of the treatment solution.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1
．． 11-hydroxyethylidene-3,03,21,1-
Sodium sulfite diphosphonate 4.0 4.4 Potassium carbonate A 30.0 37.
0 Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N-ethyl-N-β-hydroxyethylamino]-2-Methylaniline sulfate (bleach solution) Sodium ferric ethylenediaminetetraacetic acid trihydrate Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Aqueous ammonia (27g) Add water (fixer) 1.0L 10.05 Mother liquor (g) 100.0 10.0 140.0 30.0 6.5m 1 , OL 6.0 0.7 2.8 5.5 1.0L 10.10 Replenisher (g) 120.0 11.0 160.0 4, Qtnl 1, OL 5.7 Ethylenediaminetetraacetic acid disodium salt sulfite Sodium bisulfite sodium ammonium thiosulfate aqueous solution (70%) Add water (stabilizing solution) Formalin (37%) Polyoxyethylene-p- monononylphenyl nityl (average degree of polymerization 10) Add ethylenediaminetetraacetic acid disodium salt solution Mother liquor (gl 7.0 5.0 17Q, Qm 1, OL 6.7 Mother liquor (gl 2.0ml 0.3 0.05 Replenishment solution (gl O17 5.5 200.0M 1, OL 6.6 Replenishment solution (gl 3, ON 10 cartridge negatives have a magnification of 6.5x, 126 cartridge negatives have a magnification of 3.4x, cartridge negatives of the present invention have a magnification of 3.3x, and Fuji Color Super HG Paper is used to ensure that the final print size is almost the same. printed on.

These prints were observed by 15 men and 15 men, and a psychological evaluation of the image quality was conducted. The results are shown in Table-3.

Table 3 shows that the photographic material housed in the cartridge according to the present invention can provide prints with extremely good graininess, improved sharpness, and a favorable screen aspect ratio.

0.08 1, OL 1. OL 5.0-8.0 5.0-8.0 The obtained negative film was enlarged and examined to obtain five undercoated sections. - A multilayer color photosensitive material 101 was prepared by coating layers having the compositions shown below on an acid cellulose film support.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/m', and for silver halide and colloidal silver, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver 0.16 Solmer 4 0.14 gelatin
2.0 Sol Mar 5
0.07Cpd-30,2 Solmer 3 0.02Solmer 1 0.03Solv-20,25 2nd layer (intermediate layer) Fine grain silver bromide (average particle size 0.07 μm) 0.15
Gelatin 1.3 No. 36 (low-sensitivity red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 4.9 molti, average grain size 0)
．． Coefficient of variation per particle size of 5 μm (hereinafter simply referred to as coefficient of variation) 19%) 1.5 Gelatin 2,2E x S -1
4,0X10-' E x S -22,0X10-' E x S -30,6X10-' ExC-10,7 Exc-20,06 ExC-30,02 Cpd-10,01 Solv-10,8 Solv- 30,06 Solv-20,2! 3o1mer 50.08 Solv-40.1 4th layer (high sensitivity red-sensitive emulsion layer) Em-4 Silver amount 1.2 Gelatin 1.9ExS-16
X10-' ExS-23
-50,01 Solv-20,3 Solv-30,02 tIfI5# (intermediate #) Gelatin 0.7Cpd-20
,05 Solv-30,01 6th layer (low-sensitivity green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 5 molt, average grain size 0.3
μm, coefficient of variation x 9%) Monodisperse silver iodobromide emulsion (silver iodide 7
Soluchi, average particle size Q, 5 fims coefficient of variation 20%) Gelatin F, xS-4 xS-5 xS-6 Ex M-6 xM-7 xM-8 xC-9 Solmer 2 Solmer 1 Solmer 4 Solmer 3 Solmer 5 7th layer [high-sensitivity green-sensitive emulsion layer] Em-5 Silver amount gelatin x S-4 0,4 0,8 1,9 2X 10'-' 8 X 10-4 2 X 10-4 0.17 0.4 0.16 0.05 1.3 0.02 0.12 0.03 0.02 0.8 1.1 1.4 X 10-' xS-5 xS-6 E x M - 7 Low-speed blue-sensitive emulsion NI) Monodispersed silver iodobromide emulsion (silver iodide 8 molt, average grain size 0.3
μm1 coefficient of variation 20%) 5.6X10-' 1.4 ,2 0,04 0,3 Monodisperse silver iodobromide emulsion (silver iodide 5 molt, average grain size 0.6
/Am, coefficient of variation 17%) Gelatin ExS-7 ExS-8 ExY-N.

XC-3 olv-1 olv-2 olv-3 Solmer 4 10th layer (high sensitivity blue-sensitive emulsion layer) Em-6 Silver amount gelatin ExS-7 ExS-8 ExY-10 Solmer 1 xC-3 olv-3 0,3 2,8 3X 10-'3X10" 1.2 0.05 o, oos O03 0,05 0,8 1,7 2X I O-' 2 X 10-' 0.4 0.02 0.02 Sol Mer 2 Sol Mer 4 11th layer (first protection increase) Fine grain silver iodobromide emulsion (silver iodide 5 molch, average grain size 0.0
7 μm) Gelatin pd-3 pd-4 pd-5 pd-6 Solmer olv-3 Solmer 4 12th layer (second protection rei) Gelatin polymethyl methacrylate particles (diameter 1.5 μm) pd
-8 Solmer 1 Solmer 3 Solmer 4 0.03 0.33 0.8 0.1 0.1 0.1 0.1 0.05 0.05 0.13 0.2 0.5 0.05 0.03 0.05 In addition, ExS-1 to which surfactant Cpd-7 and hardening agent H-1 were added: ExS-4: ExS-2: Ex S-5: ExS-3: EXS-6: ( CH2)3So,'' (CH2)3S03Nm ExS-7: EXS-8: ExC-4: 0cH2CONHcH2cH20cH xC-2 xM-5 t ExC-5: ExC-1: C5H,, (t) Ex M -7 xM -8 H t t ExY-1 xC- p H p C4H7(t) xC-9 H H pd-5 SOImer 2H5 Sol Mar2 Solv-5 pd-7 pd-8 CH2-cH-802-CH2 C) Sample 301 and Sample 303 were prepared using emulsions showing I2=CH-8o2-CH2 E m -4e 5 and 6 in Table IK.

The contents are shown in Table 4.

Shishi-4 Sample 301 is placed in the cartridge shown in 2nd rA.
Sample 401 was obtained by photographing a sample, leaving it for 2 days at 25°C and relative humidity of 52°C, and sealing it in a 120w x 60am moisture-proof film under the same conditions. The screen size of this cartridge is 24fiX36f11.

Sample 302 was processed in the same manner to obtain sample 402.

Using Sample 401 and Sample 402, the same subject was photographed at different distances.

The A photophosphorus film obtained as described above was processed using an automatic processor in the manner described below (until the cumulative replenishment amount of the bleach-fix solution became three times the volume of the mother liquor tank).

Processing method Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38℃ 45mj IO
L bleach 1 minute 00 seconds 38℃ 20tnl
4L bleach fixing 3 minutes 15 seconds 38℃ 30
ν 8L water washing (1140 seconds 35℃ 4L counter-current piping type from (2) to (11).

Wash with water (2) 1 minute 00 seconds 35°C 301! Lt4I.

Stable 4 (1 second 38℃ 2Qrnl
4L drying 1 minute 15 seconds 55°C The replenishment amount is 35 m wide and 1 m long.Next, write down the composition of 1 treatment solution.

(Color developer) Mother solution (g) Replenisher (gl diethylenetriaminepentaacetic acid 1.
0 1.11-hydroxyethylidene-3,03,2
Sodium 1,1-diphosphonic acid pentoxide 4.0 4.4
Potassium carbonate 30.0
37.0 Potassium Bromide 1.4 0
．． 7 Potassium iodide 1.5■ Hydroxylamine sulfate 2.4 2
．． 84-[N-ethyl-N-β-4,55,5hydroxyethylamino]-2-methylaniline sulfate solution was added 1. OL 1.0Lp
) (lo, o s l 010 (bleaching solution) common to mother liquor and replenisher (unit: g) ethylenediaminetetraacetic acid ferric 120.0 ammonium dihydrate ethylenediaminetetraacetic acid disodium 10.0 lium ammonium chloride bromide 100.0 Ammonium Nitrate 10.0 Bleach Accelerator
o, oos mole ammonia water (
27%] 15.■l Add water 1.0L-6.3 (Bleach-fix solution) Common to mother liquor and replenisher (unit: g) Ferric ethylenediaminetetraacetate 50.0 Ammonium dihydrate Ethylenediaminetetraacetic acid disodium 5.0 Lium salt Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution 240.01117 (70%) Ammonia water (27%) Add 6.0m water 1.05%4
7.2 (Washing solution) Mother liquor and replenisher Common tap water is used with H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas). Water was passed through a mixed bed column packed with water to reduce the concentration of calcium and magnesium ions to 3 rxq/L or less, and then 2019/L of sodium incyanurate dichloride and 0.15 g/L of sodium sulfate were added.

The - of this liquid was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (3
7th) 2.0-unit polyoxyethylene-P-°0.3 monononylphenyl ether (average degree of polymerization 10) Add 0.05 thorium salt water to ethylenediaminetetraacetic acid 1. OL voice
5.0-8.0 pH 6.3 Long-distance photographic negatives were cut to form the same sheet to produce negatives of different sizes. Prints of the same size were made from these negatives by adjusting the enlargement magnification, and the results are shown in Figure 5.

Table 5 Evaluation of effective screen area l) Legend for 2) with print area of 94 cm 0: Good Δ: Slightly poor In order to provide the print quality that can be achieved, the negative size needs to be 3 crrL2 or more, preferably 6α2 or more.

[Brief explanation of drawings]

FIG. 1 shows the positional relationship between the cartridge of the present invention and the camera. If-j: Cartridge of the present invention, 2 represents a camera compatible with it. FIG. 2 represents the cartridge of the invention from the front. FIG. 3 shows the film and light-shielding paper inserted into the cartridge of the present invention. 3 represents a film (width 35, OM, length 550 m), and 4 represents a light-shielding paper (width 35°2'Els length 950 m). Engraving of the drawings (no changes to the contents) Procedural amendments, figure 1, case display Heisei/year patent application number! 6t/No. 2, name of the invention Silver halide 5 photosensitive material stored in a cartridge 3
We will submit the revised figure 5, the subject of the amendment: all documents and drawings 6, the contents of the amendment and the engraving of the drawings (no changes to the contents).

Claims (1)

[Claims] In a silver halide photographic light-sensitive material housed in a cartridge, at least one of the light-sensitive silver halide emulsion layers of the light-sensitive material contains an inner core consisting essentially of silver bromide and/or silver iodobromide; Contains a negative silver halide grain having a plurality of outer shells provided outside an inner core and consisting essentially of silver bromide and/or silver iodobromide, and the outermost shell of the silver halide grain The iodine content of the outermost shell is 10 mol% or less, and the iodine content is 6 mol% lower than that of the outermost shell.
an iodine-rich shell having a higher iodine content is provided inside the outermost shell, an intermediate shell having an iodine content intermediate between these two shells is provided between the outermost shell and the iodine-rich shell; The cartridge contains a silver halide emulsion in which the intermediate shell has an iodine content higher than the outermost shell by 3 mol% or more, and the iodine-rich shell has an iodine content higher than the intermediate shell by 3 mol% or more, and consists of a film roll chamber that stores a roll of unexposed photosensitive material, a take-up chamber that winds up exposed photosensitive material, and a bridge section that connects them and has an opening, and further includes a film roll chamber that stores a roll of unexposed photosensitive material, and a bridge section that connects them and has an opening. to be done1
Effective screen area per frame is 3.0cm^2 or more 25.0
cm^2 or less, and a silver halide photograph housed in a cartridge, characterized in that the ratio of the length of the long side to the length of the short side of the screen of one frame is 1.2 or more and 2.0 or less. photosensitive material.