JPS6232443A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a high contrast image having high sensitivity and high maximum density by using a photosensitive silver halide emulsion contg. flat silver halide particles having a specified ratio of diameter/thickness and coated with an epitaxially grown silver salt. CONSTITUTION:A silver salt is epitaxially grown on the surfaces of flat silver halide host particles having >=5 ratio of diameter/thickness. A mixed emulsion contg. the flat epitaxial particles and internally fogged silver halide particles is applied to a support and coated with a protective layer. Thus, relative sensitivity and maximum density are increased by processing at a low temp. and development is accelerated.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel silver halide photographic light-sensitive material, and more specifically, it provides high sensitivity, high contrast, and high maximum density images, and has remarkable development characteristics. This invention relates to an improved silver halide photographic material.

(Prior Art) Regarding photographic images made of silver, the ratio of the optical density of the image to the amount of silver per unit area constituting the image is generally called covering power.
It is used as a measure of the optical efficiency of the silver that makes up the image. Generally, the covering power of a silver halide photographic light-sensitive layer increases as the size of the silver halide grains becomes smaller, and decreases as the grain size increases. - In general, the sensitivity of a silver halide emulsion layer increases as the size of the silver halide grains increases, so silver halide emulsions with large grain sizes are used in highly sensitive photographic materials. Therefore, high-sensitivity photographic materials require a large amount of silver per unit area to obtain a constant image density. In other words, in order to achieve both high sensitivity and the required maximum image density, more silver salt must be contained per unit area on the photographic light-sensitive material. This has been the actual situation with conventional high-sensitivity photographic materials.

(Problems to be Solved by the Invention) As an attempt to improve covering power while maintaining high sensitivity, a technique for adding various polymers to a high-sensitivity coarse-grained silver halide emulsion was disclosed in British Patent No. 7゜o4t♂. , θj No. 7,
No. 1,03, No. 4t7/, U.S. Patent No. 3,0 Ko 3.
No. 97, Nos. 3 and 4, and No. 6/r. All of these have the effect of slightly increasing the covering power, but are not sufficient, and may weaken the strength of the coating film, which is not preferable. In particular, in the automatic processors commonly used today, if a weak coating film is used, some of the gelatin in the film will dissolve into the developer or fixer and adhere to the automatic developer's conveyance roller, causing the photosensitive material to become exposed. This has the disadvantage of being transferred to the material and causing contamination of the photographic image.

On the other hand, U.S. Patent No. J, ? ? , <, j/2 and 3.
/77.212 each specification uses a silver halide photographic light-sensitive material in which surface latent image type silver halide coarse grains and silver halide fine grains having internal fog nuclei (i-) are supported in the same 1j or adjacent layer. It is described that photographic images with high sensitivity, high contrast, and high covering power can be obtained using the method.

However, this method has the drawback that it requires a long development time in normal low-temperature processing to obtain sufficient high sensitivity, high density, and high contrast, and that the desired effect does not occur in normal high-temperature rapid processing. have.

In order to improve these drawbacks, attempts have been made to introduce various additives such as rhodan, imidazoles, and thioethers into the sensitive materials and processing solutions. (For example, U.S. Pat.
It is described in the Meiji A of No. jJj and No. J7-1-74T. ) Furthermore, tabular silver halide grains having a ratio of grain size to grain thickness of 5 or more are used as the photosensitive silver halide grains in the above-mentioned light-sensitive material (for example, Japanese Patent Application Laid-Open No. 2003-2013), Improvements have been made in sensitivity, covering power, and development characteristics. However, these improved methods still require a long development time to obtain high sensitivity, high covering power, and high contrast, and cannot be said to be fully suitable for rapid processing.

Accordingly, one object of the present invention is to provide a silver halide photographic material that provides images with high sensitivity, high contrast, and high maximum density.

Another object of the present invention is to shorten the development time in low temperature processing and to provide a high temperature rapid processing suitability.

The inventors of the present invention conducted extensive research to achieve the above object, and found that the following photographic materials can be used to achieve continuous production.

That is, a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support contains a light-sensitive silver halide emulsion and an internal fogged silver halide emulsion, and the light-sensitive silver halide The silver halide grains contained in the emulsion are tabular silver halide grains whose grain size is equal to the grain thickness j, and the silver halide grains are hybrid grains in which a silver salt is epitaxially grown on the surface of the tabular grains. I found out.

In the present invention, "photosensitive" means that the sensitivity of a photosensitive silver halide emulsion is higher than that of an internally fogged silver halide emulsion. More specifically, it is more than 70 times the sensitivity of the internal fogged silver halide emulsion, more preferably 1
(~〈 means having a sensitivity of 00 times or more.

The sensitivity here is defined in the same way as the sensitivity shown below.

As the photosensitive silver halide emulsion, a conventional silver halide emulsion such as a surface latent image type emulsion is used.

Here, the surface latent image shop's silver halide emulsion is l~//
/00 seconds After exposure, when developed by the method of surface development (A) and method of internal development (B) shown below, the surface development (
The emulsion is an emulsion in which the sensitivity obtained by internal development (CB) is higher than that obtained by internal development (CB), preferably an emulsion in which the sensitivity of the former is at least twice that of the latter. Here the sensitivity is as follows:
defined.

Eh S is sensitivity, Eh is maximum density (Dmax) and minimum density (D
It shows the exposure amount required to obtain @[7(Dmax+Dmin), which is exactly in the middle of min).

[Surface development (A)]

Developed for 70 minutes at a temperature of θaC in a developer having the following formulation.

N-methyl-p-aminophenol (hemisulfate) 2. jf ascorbic acid ioy sodium metaborate tetrahydrate 3jf potassium bromide
if add water
[Internal development (B)] Red blood salt 31/1 and phenosafranin 0.0/26t/-
The sample was treated in a bleaching solution containing E for 10 minutes at about θ0C, then washed with water for 70 minutes, and developed for io minutes at 20C in a developer having the following formulation.

N-methyl-p-7 minophenol (hemisulfate) 2. jf Ascorbic acid 10f Sodium metabolate tetrahydrate 3! ? potassium bromide
l? Sodium thiosulfate
31 Add water
/-13 The photosensitive silver halide emulsion of the present invention is a silver halide emulsion containing hybrid grains in which a silver salt is epitaxially grown on the surface of tabular silver halide grains, which will subsequently serve as a substrate for epitaxial growth. The particles are called host particles. Further, a host particle and a hybrid particle epitaxially grown on its surface are simply called an epitaxial envelope.

The proportion of tabular epitaxial grains used is:
It is preferably 20% by weight or more based on the entire photosensitive silver halide grains, more preferably jOX! % or more. The grains other than the tabular epitaxial grains may be non-tabular grains, tabular grains, or non-planar epitaxial grains, or they may coexist.

Next, the tabular silver halide host grains used in the present invention will be described.

The tabular silver halide host grains of the present invention have a diameter/
The thickness ratio is 1 or more, preferably 5 or more and 100 or less, more preferably! Above and below SO.

Particularly preferably, it is 2 or more and 20 or less.

The diameter of a tabular silver halide host grain herein refers to the diameter of a circle having an area equal to the projected area of one grain. In the present invention, the diameter of the tabular silver halide host grains is preferably Q, jk10μ, more preferably o, r~1.0μ,
Particularly preferred are /, θ to Hiro, and Oμ.

In general, tabular silver halide host grains are tabular with two parallel planes, and therefore "thickness" in the present invention refers to the thickness of the two parallel planes constituting the tabular silver halide host grains. expressed in distance.

The silver iodide composition of the tabular silver halide host grains is preferably silver bromide or silver iodobromide, and the silver iodide content is preferably θ to 30 mol, and the silver iodide content is preferably θ to 70 mol. Silver iodobromide is preferred.

Next, a method for producing tabular silver halide host grains will be described.

The tabular silver halide host grains can be produced by appropriately combining methods known in the art.

For example, in an atmosphere with a relatively high pAg value of pBr t ,j or less, seed crystals containing tabular grains of at least 100 yen (by weight) are formed, and silver and halogen solutions are simultaneously added while maintaining the pBr value at the same level. It is obtained by growing seed crystals.

In this grain growth process, it is desirable to add silver and halogen solution at-m so as not to generate new crystal nuclei.

The size of the tabular silver halide host grains is controlled by temperature control,
Controlling the selection of the type and amount of solvent, the silver salt used during grain growth, the addition rate of halide, etc.C;
More adjustable.

When producing the tabular silver halide host grains of the present invention, a silver halide solvent may be used as necessary to control grain size, grain shape (diameter/# ratio, etc.), grain size distribution, and grain growth rate. I can control it. The amount of solvent used is 10 to 0 flK of the reaction solution, especially 70 to 0 flK.
10XIr81 preferred.

For example, by increasing the amount of solvent used, the C2 particle size distribution can be made monodisperse and the growth rate can be increased. On the other hand, there is also a tendency for the thickness of the particles to increase with the amount of solvent used.

Often used silver halide solvents include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat. =77.1
No. 67, No. 3,790. jrZ No. J, ni 7th,
No. 62r etc. can be referred to.

During production of the tabular silver halide host grains of the present invention, in order to accelerate grain growth, the addition rate, amount, and addition fIk degree of the silver salt solution (e.g., AgNO3 aqueous solution) and halide solution (e.g., KBr aqueous solution) are increased. A method is preferably used.

These methods are described, for example, in British Patent No. 1.33,
octopus! No. 3, U.S. Patent No. 3. Otsu 72. No. 00, same $, J
, 460,7j7, same No.'4,24tλ, 4t%j
No., Tokukai Akira! Yo-/4t23 Kota, J-j-/61
/2+ can be referred to the description of the number etc.

The silver salts (hereinafter referred to as epitaxial silver salts) that are epitaxially elongated on the surfaces of tabular silver halide host grains used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, and silver chloroiodide. , silver halides such as silver iodobromide, silver chloriobromide, and
Cover with silver salts such as silver thiocyanate, silver phosphate, silver cyanide, and silver carbonate.

The coverage of the epitaxial silver salt on the surface of the tabular silver halide host grains is preferably 50% or less, particularly preferably 70% or less, and the epitaxial growth site is limited to the sides and vertices of the tabular silver halide host grains other than the main surface. It is preferable to And the growth amount of the epitaxial silver salt is 7!4 or less of the epitaxy%'A/total grain, preferably /θ
It is preferably less than 2.5 inches from the top and bottom of the engagement.

In the epitaxy/JAL method on the surface of tabular silver halide host grains used in the present invention, a water-soluble compound containing an anion of an epitaxial silver salt and a water-soluble silver salt are added by a double-jet method or a single-jet method. and conversion methods, etc., published by Tokukaisho! l-10, :r, f2t, same 39
-/62!4tθ, same! Any of the methods described in j-IO'lθ can be used. Moreover, the epitaxy silver salt is not limited to one type, and multiple types may be used. At this time, several types of epitaxial silver salts may be grown on the tabular silver halide host grains, or another type of epitaxial silver salt may be grown on the tabular silver halide host grains, and another type of epitaxial silver salt may be grown on the tabular silver halide host grains. The silver salt may be epitaxially grown.

In the present invention, when the epitaxial growth position of the silver salt on the surface of the tabular silver halide host grain is limited to the middle vertex on the edge, the epitaxial silver salt is grown in the presence of a growth site director if necessary. be able to.

Here, as the director, a stabilizer adsorbed to the surface of the tabular silver halide host grains or an adsorbent compound such as a spectral sensitizing dye can be used.

Preferred spectral sensitizing dyes are cyanine dyes, merocyanine dyes, and hemicyanine dyes. Examples include the dye ■ Anhydro-! -Kuroro 9-Ethyl! ′-phenyl-
3,3-bis(3-sulfopropyl)oxacarbocyanine hydroxide dye l Anthrota,! 'Regi-rotor ethyl-3,3-bis(3-sulfobutyl) theacarbocyanine hydroxide dye ■ Anthro rotor ethyl-3,3'-bis(3
-Sulfopropyl)-Hiroshi! ,9′,! '-Dibenzothiacarbocyanine hydroxide color XIV Anthrota,! -dichloro3,3'
-bis(3-sulfopropyl)theacyanine hydroxide dye V /, /-diethyl=λ, 2'-cyanine-p
−) Luenesulfonate, etc. can be listed. When a cyanine dye is used as a director, the amount added must be greater than the saturation adsorption amount for J band formation.

In addition to the above-mentioned tabular epitaxial grains, regular (
It may contain particles having a regular crystal shape, particles having an irregular crystal shape such as a spherical shape, or particles having a composite shape of these crystal shapes. The average grain size of these halide complex grains is preferably larger than that of a silver halide emulsion having internal fog nuclei, and particularly preferably Q is 6 μm or more. The particle size distribution may be narrow or wide.

In the process of forming silver halide host grains such as tabular epitaxial grains used in the present invention, physical ripening, and epitaxial growth, cadmium salt, zinc salt,
A lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

As the photosensitive silver halide emulsion, a so-called primitive emulsion which is not chemically sensitized can be used, but it is usually chemically sensitized.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H Freezer (H
, Frieser)
Die Grundlagen
der PhotographischenPr
ozesse mit Silver-Haioge
Niden) J (Akademische Verlagsgesel)
lschaft.

The method described on pages 67j to 734 (published in 1996) 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, thioic acid salts, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
2.4t/θ, 6/ri, 2.27#, 9nu7.

Ko, 7J/, ≦6, j, 1sj6,9! ! issue.

It is described in Da, No. 032.9λ♂ and Da, No. θj7.74tθ. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Patent U, 4t♂7. ? jθ No., Ko, E/9.97
No. 9, Ko! /r, ≦9! No., Ko, Wa! 3. No. 09,
Ko-ri? 3. 70, Ko, 6 free, 637% 3. 30, J'47, a, ory, ate.

For noble metal sensitization, in addition to total complex salts, complex salts of metals in Group 1 of the periodic table, such as platinum, iridium, and palladium, can be used; specific examples thereof are given in US Pat.

No. 399, OF2, tt4tr, olhθ, British Patent t/Jr, 06y, etc.

Various hydrophilic colloids can be used as binders in the photographic material of the present invention.

Colloids used for this purpose include, for example, gelatin, colloidal albumin, polysankara ide, cellulose derivatives, synthetic resins, polyvinyl compounds including polyvinyl alcohol derivatives, acrylamide polymers, and hydrophilic colloids commonly used in the photographic field. can be mentioned. Along with hydrophilic colloids, hydrophobic colloids such as dispersed polymeric vinyl compounds, especially those which increase the dimensional stability of the photographic material, can be included. Suitable compounds of this type include water-insoluble polymers made by combining vinyl heptanomers such as alkyl acrylates or alkyl methacrylates, acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. Those compounds are Hiro-hydroxy-6-methyl-7°! , 3a,7-chitrasaindene, 3-methyl-benzof7zole, /-phenyl-! -Many 'vJs, including mercaptotetrazole
A very large number of compounds have been known for a long time, including ring compounds, mercury-containing compounds, mercapto compounds, and metal salts.

An example of a compound that can be used is K. Mees and “The
Theory of the Photography
hicProcess'' (3rd edition, 7936), citing the original document.

The following C2 silver halide emulsion containing fog nuclei inside to be used in the light-sensitive material of the present invention is, for example, 217
A test piece coated on a C2 transparent support so as to have a thickness of 3.0 m2 was coated with D-i9 (a developer specified by Eastman Kodak Company) without being exposed to light. tOC, θ when the force is applied for 2 minutes, ! The following transmission fog density (excluding the density of the support itself) was given, and potassium iodide was added to D-/9 without light.
When developing 3joc with a developer added to j t/13 and developing a dark color by a minute.

An emulsion giving a transmission cuff density of 0 or more (excluding the density of the support itself) is used.

Iron halide emulsions having capri cores inside can be prepared by various known methods. U.S. Pat. No. 2.J9, U.S. Pat. ? ? 4. j/, the method described in Specification No. 2, or by first fogging under conditions of low pAg and high pH, or chemically fogging with a reducing agent, a gold compound, or a sulfur-containing compound. 1, a core emulsion is prepared, and then a shell emulsion is deposited around the core emulsion (U.S. Pat. No. 3,2θt,
(See the core-shell emulsion technique described in No. 313)
, Tokukai Akira! ? The method described in -2/74g No. 7 specification,
There is a method in which the interior and surface of silver halide grains are covered together, and then the fog nuclei on the surface are bleached with a red blood salt solution or the like.

A silver halide emulsion having internal fog nuclei has a smaller average grain size than a surface latent image type silver halide emulsion, and has the following characteristics:1. θ~0. Those with an average particle size of Oj μm are preferred, and those with an average particle size of 0.6 to 0.7 μm are more preferred, θ,! Particularly preferred is one below μm, giving good results.

In the present invention, the grain size of silver halide is expressed by the grain diameter in the case of spherical or approximately spherical grains, and in the case of grains of other shapes (for example, cubes, flat plates, etc.), it is the diameter of a sphere with the same volume. I will express it.

The internal secondary silver halide emulsion may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride, and the like.

The content ratio of the photosensitive silver halide and the internal fogged silver halide in the silver halide photographic material of the present invention depends on the emulsion type used (for example, halogen composition), the type or purpose of the photosensitive material used, Although it can be changed depending on the contrast of the emulsion used, preferably lθ
0:/ to l:ioo, especially /Q:/ to l:l
θ is preferable. Also, as a coated iron lid, 0.
1 to tOf/m is preferable.

Several embodiments are possible regarding the layer structure of the photographic material according to the invention. Representative ones are shown below. ■Construction in which a mixed emulsion of the tabular epitaxial grains of the present invention and internally covered silver halide grains is spread 1:j4 on a support, and a protective layer is coated thereon.■First, the internally covered silver halide grains are coated. A structure in which an emulsion containing silver particles is coated on a support, an emulsion containing tabular epitaxial grains of the present invention is coated on the support, and a protective layer is further coated on top of the emulsion. A mixed emulsion of epitaxial grains and internally covered silver halide grains is coated on a support, an emulsion containing the tabular epitaxial grains of the present invention is coated on top of that, and a protective layer is further coated on top of that. A mixed emulsion of the tabular epitaxial grains of the present invention, ordinary photosensitive silver halide grains, and internally capped silver halide grains is coated on a support, and a protective layer is coated thereon. Structure: First, a mixed emulsion of the tabular epitaxial grains of the present invention and a silver halide emulsion with internal fogging is coated on a support, a conventional photosensitive silver halide emulsion is coated on top of that, and then A structure in which a protective layer is coated thereon: (1) First, an emulsion containing internally covered silver halide grains is coated on a support, and an emulsion containing tabular epitaxial grains of the present invention is coated thereon; What about a structure where an emulsion containing ordinary photosensitive silver halide grains is coated on top of that, and then a protective layer is coated on top of that? can be mentioned.

However, the structure is not limited to these, and the support may have the above structure on both sides, or the silver halide emulsion layer may be separated into three or more emulsion layers with different spectral sensitivity distributions. It's okay.

The light-sensitive material of the present invention includes tetrazaindenes having at least one mercapto group, purines having at least seven mercapto groups, triazaindenes having at least one mercapto group, and phtazaindenes having at least one mercapto group. Developing in the presence of one or more of these is effective in preventing fogging and uneven staining. Specific examples of these compounds include the following.

R addition amount is /X10 ~/X/θ 1 mol-silver halide, preferably <, /X/θ-4 ~/X
/0-2 mol 1 mol-halogen ratio silver is preferred.

Further, in the light-sensitive material of the present invention, elliptical image formation can be promoted by using a metal compound represented by the following general formula (I) in combination with any of the constituent elements on the support.

General formula (1) %formula% [In the formula, person/B may be the same or different.

Alkyl group, aralkyl group, aryl group, heterocyclic group,
or -3-R, (R represents an alkyl group, an aryl group, an aralkyl group, a Peter group, or an amine group). ] These compounds are distinguished by t, for example -t.

The protective layer of the silver halide photosensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one mentioned in AI.

Further, the protective layer may be a single layer or may be a single layer.

A matting agent and/or a smoothing agent may be added to the emulsion or protective layer of the silver halide photographic material of the present invention, preferably to the M retention layer. Examples of matting agents include those with a suitable particle size (particle size θ, 3 to J'μ, or those with a particle size of 3 to J'μ),
An organic compound such as a water-dispersible vinyl polymer such as polymethyl methacrylate, or a silver halide, barium strontium sulfate, etc., which is at least twice the thickness of the layer, particularly preferred is a layer with a thickness of 7). Inorganic compounds such as the following are preferred. Smoothing agents help prevent adhesion failure similar to matting agents, and are particularly effective in improving the frictional properties of motion picture film related to camera compatibility during shooting or projection; specific examples include liquid paraffin,
Waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, silicones such as polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes, or their alkylene oxide adducts. etc. are preferably used.

The silver halide photographic light-sensitive material of the present invention further includes an antihalation layer and an intermediate layer, if necessary.

A single layer of filters, etc. can be provided.

In the photographic material of the present invention, the photographic silver halide emulsion layer and other hydrophilic colloids Jω can be hardened with any suitable hardener. These hardeners include JP-A-Sho J'
! -7tθ2! No. J3-7602 Otsu and Ta 3-7
7≦/vinylsulfonyl compounds as described in No. D;
Hardeners having active halogens; dioxane wire conductors; oxypolysaccharides such as oxy starch powder, etc. are included.

The photographic silver halide emulsion layer may contain additives useful for photographic emulsions, such as moisturizers, sensitizers, light-absorbing dyes, plasticizers, and the like.

The light-sensitive material of the present invention may contain water-soluble dyes as filter dyes in hydrophilic colors, or for various purposes such as prevention of radiation exposure and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

The photosensitive material of the present invention may contain a surfactant for various purposes. Depending on the purpose, any of nonionic, ionic and amphoteric surfactants can be used, such as polyoxyalkylene 84, amphoteric amino a<including sulfobetaines), and the like.

In the light-sensitive material of the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing color.

The epitaxial growth site indicator of the tabular silver halide hybrid grains used in the present invention is used as a spectral sensitizer, and as it is,
Or you can refill it and use it.

Cyanine dye and merocyanine color as sensitizing dyes! , complex cyanine dyes, complex merocyanine dyes, holophoradianine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

Sensitizing dyes useful in the present invention include, for example, Research φ Disclosure Vol. 726, /T6/7/;QJ
(/97r, December), Section iv.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working silver halide emulsions. especially,
It is advantageous to use the pigment at a dye density that does not significantly reduce the inherent sensitivity of the silver halide emulsion. of sensitizing dye per mole of silver halide.

0X10 ~ approximately X/θ mole, especially FJ4txlθ of sensitizing dye per mole of silver halide ~, jX10-
It is preferable to use a portion of 4 moles.

In the photographic JCG optical material of the present invention, the photographic emulsion JC Haruka or other J- is plated on one or both sides of a flexible support commonly used in photographic light-sensitive materials. Examples of useful flexible supports include cellulose acetate, vinegar [ml], films made of synthetic polymers such as cellulose and polyethylene terephthalate, baryta layers, or α-olefin polymers (←IJ is polyethylene, etc.). Cover with coated or laminated paper.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. U.S. Patent Co., l;r/,
2 dehiro issue, same co, 7dl, 797, same 3. The method described in Tako 6, Ta 2/No. 12 is an advantageous method.

The present invention can be used with any photographic material that requires high sensitivity or high contrast. For example, XM3 photographic material, lithium type photographic material, black and white negative photographic material, color negative photographic material,
It is engraved on color, e-photosensitive materials, etc.

Photographic processing g2 of the light-sensitive material of the present invention is, for example, research
Disclosure (Research Di 5clo)
sure) / No. 76 f, xr ~3oj! Any of the known methods and known treatment liquids as described in L(几D-t7t4tJ') can be applied. Depending on the purpose, this photographic processing may be either a photographic processing that forms a recorded image (black and white photographic processing) or a photographic processing that forms a dye image (color photographic processing). Is the processing temperature normal/? From 0C! The temperature is chosen between 0°C, but it may be lower than 0°C or even higher than 0°C.

For example, in the case of black-and-white photographic processing, a C two-component developer can contain known developing agents.

As the main developer, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. /-
phenyl-3-virazolid/), aminophenols (
For example, N-methyl-p-aminophenol), etc.
They can be used alone or in combination. The photographic processing of the light-sensitive material of the present invention is a patent application! -/taj4t,!
It is also possible to process with a developing solution containing imidazoles as a silver halide solvent as described in No. 12. It is also possible to process a working solution containing a silver halide solvent described in Japanese Patent Application Shota J-/Jj, No. 7.67 (2), an additive such as an indazole or a triazole, and gold. 2 contains general preservatives, alkaline agents, pH buffers, antifoggants, etc., and 1 color toning agent, development accelerator, surfactant, eraser, etc. It may also contain foaming agents, water softeners, hardeners, viscosity-imparting agents, and the like.

(Example) Next, the present invention will be specifically explained according to examples.

Example 1 (1) Non-tabular silver iodobromide host emulsion (AgI = 4 mol%) Em-A Aqueous gelatin solution (: Aqueous silver nitrate solution and aqueous potassium bromide and potassium iodide solutions were subjected to constant potential double Particles are formed by the jet method by adding a set amount and the second stage accelerated flow rate addition C2, and desalted by the precipitation method G2 to obtain an average particle size of 1.
18m silver iodobromide host emulsion (A g I
= 6 mol qb>Em-A was obtained.

(2) Tabular silver iodobromide host emulsion (I-6 Molch)
...E m -B and B' 0.0 rmol/! A gelatin aqueous solution containing 2 potassium bromide and a dinitric acid chain aqueous solution and an aqueous solution of potassium bromide and potassium iodide were added using a double jet method. For the silver nitrate aqueous solution whose pBr was maintained at 7./ until the end of the silver addition, and the potassium bromide and potassium iodide aqueous solutions, the total amount of Tamorchi was added quantitatively in the first stage, and the remaining glue was added! Particle formation was carried out by adding CH at a second stage accelerated flow rate. Desalted by precipitation method, average particle size 1.6 μm, thickness 0.10 μm particle size/
An emulsion B m -B with a thickness ratio of /j and 2 was obtained. Em-
13t sodium dithiosulfate/θm9/AgmoJ3,
Gold chloride (-@t o lay / Agmo-g) was added for chemical sensitization, followed by anhydro-terchloro-terethyl-t'-phenyl-J, 3'-bis(3-sulfopropyl)oxacal rF, cyanine hydroxide. Triethylamine salt (color X1) 10 mol/A g m
og and spectrally sensitized to obtain a photosensitive emulsion-B'.

(3) Tabular silver iodochloride host emulsion (AgI=damorti)...E m -C and C1 0.0 t mol/! An aqueous gelatin solution containing potassium bromide and ammonia, an aqueous silver nitrate solution, and an aqueous solution of potassium bromide and potassium iodide were added using a double jet method. Silver nitrate aqueous solution, potassium bromide, and potassium iodide aqueous solution were added at a fixed rate of 5 mol% of the total amount added in the first stage, and the remaining amount was 5%. ! Then, a λ stage acceleration flow rate was added and particle shape g was performed.

Desalted by precipitation method C, average particle size t, Qμm thickness 0. t
4tθμm, particle size/thickness ratio 7. /4 emulsion E m -C
I got it. The same amount of thiosulfate as E m -Cl2 and E m -B') was chemically sensitized by adding IJ and chloroauric acid, and dye I was added and spectral sensitized to form a photosensitive emulsion E In-C. '
I got it.

(4) Epitaxial growth of silver chloride on the surface of non-tabular silver iodobromide crystal grains (Em-D) A non-tabular silver iodobromide host emulsion (Km-A) was grown using silver nitrate and sodium chloride, i) Ag -7.l.

An aqueous ζ-disilver nitrate solution and an aqueous sodium chloride solution were added using a double jet method to grow epitaxial silver chloride containing the entire amount of silver halide. Epitaxy silver chloride was randomly grown all over the host grains.

Non-tabular silver iodobromide grains in which silver chloride was epitaxially grown were chemically sensitized by adding chloroauric acid and sodium thiosulfate in the same amount as g m -B', and spectrally sensitized by adding dye 17 to form a photosensitive emulsion. E m -D was obtained.

(5) Epitaxial growth of silver chloride on the surface of tabular silver iodobromide host grains... (Em E) Tabular silver iodobromide host emulsion (Em-B) E m -A of (4) above
Similarly, Sini- and Tamorchi epitaxial silver chloride was grown using the same method instead of . Epitaxy silver chloride had grown over the entire main surface of the host grain. Example(
Chemical sensitization and spectral sensitization were performed in the same manner as in 4) to obtain a photosensitive emulsion (Em-E).

(6) Epitaxial growth of silver chloride on restricted positions on tabular silver iodobromide host grains (Em-F) (5)
Similar to I:, silver chloride was epitaxially grown and chemically sensitized.

However, as a sensitizing dye It-director, pAgy4
After stirring for 10 minutes, a silver nitrate aqueous solution and a sodium chloride aqueous solution were added for epitaxial growth.

By the above method, a photosensitive emulsion E m -F in which silver chloride was epitaxially grown on the tops of tabular silver iodobromide host grains was obtained.

(7) Epitaxial growth of silver chloride on restricted positions on tabular silver iodobromide host grains...E m -G
(6l: I2E instead of host emulsion (Em-B) in
Similar to (6) using m-C; director (
After adding the dye (■), silver chloride was epitaxially grown and a post-ripening process was carried out. By the above method, a photosensitive emulsion E m -G in which apex C of tabular silver iodobromide host grains: silver chloride was epitaxially grown was obtained.

(9) Internal fogged silver halide emulsion (Em-H)
Example 2 of U.S. Pat. No. 2592.23-0/In a similar manner to
A silver chlorobromide emulsion (A gCl : comol ts) of μ was prepared and irradiated with light to obtain a silver chlorobromide emulsion E m −)(t-) with an internal fog.

4. Preparation of coating sample An emulsion layer consisting of each of the above-mentioned photosensitive emulsions Em-E, F, and O as a single emulsion and a protective layer of an aqueous gelatin solution were coated separately on a subbed polyester base C; uniformly≦Y sequentially. Then, dry and apply the sample. What is the amount of coated silver in the 0 coated sample after all fabrication? , the amount of gelatin applied is milk jljJ (t for j, j S'/tn2
W'imM ``'CO, tP7m2.

Next I: Sensitive emulsion E m -B', C', D, E, F,
An emulsion layer prepared by mixing the internal cover emulsion E m -H in 3θ mold on Q and a protective layer of gelatin aqueous solution similar to the above were subbed and coated separately on the 7c polyester base in ζ-bi-uniform-ζ-bi sequential manner and dried. Let, coated sample /, -13,!
, 2.9 was created. The amount of coated silver in the coated sample was 1.
017m2.

The amount of coated gelatin is emulsion 1f.3 / , j 7. /m
2. θ in the Ho\U layer! f/m.

(Iη Development progress +11 was prepared, fc Ikebu samples 1 to d were exposed to wedge light, and then developed using the following developing solution A+2 at 20°C for 7 minutes, 2 minutes, and Hiromin, respectively.

Sensitometry was performed on sample C: stopped, fixed, swam, and dried. The results are shown in Table 1.

Jj (S) is the fogging → -0,2 to obtain the transmitted light spotting density. It is shown by the slope between Kaburi 10, / and Kaburi 10, Yu.

Development iA treatment / - Phenyl-3-pyrazolidone 0.5J Hydroquinone - 〇, Og ethylenediamine di-sodium acetate λ, Of potassium sulfite to, oy Boric acid
Da, 0? potassium carbonate
−〇、θ? sodium bromide
20. Of diethylene glycol
As shown in Table 1, as shown in Table 1, coating sample AI of a mixed emulsion of a flat plate epitaxial emulsion and an internally fogged emulsion.

7. Comparing the other samples, the highest relative sensitivity increased when treated at low temperatures. Also, coated sample waste%
A particularly remarkable feature of 2.912 is that the development progresses quickly. The coated sample was developed for 2 minutes to bring out the desired photographic characteristics such as sensitivity, density, and gamma.
The k degree and gamma value did not change significantly, but the fog increased.≦2 In comparison, the other coated samples did not sufficiently bring out the quality of the photograph after 2 minutes of development. Among the flat epitaxial emulsions, a mixed emulsion of an emulsion with limited growth using a director and an internally fogged emulsion was coated with 45 samples, 7g67, and a mixed emulsion of a flat plate epitaxial emulsion without using a director and an internally fogged emulsion was coated. Coating sample A6. Comparing the two, the sensitivity, maximum degree, and gamma have increased, and the development progress has become faster.

Example 2 (1) Epitaxial growth of silver chloride on restricted positions on tabular silver iodobromide host grains...E rn
-1 and coating samples were added to gelatin water bath GL dinitrate aqueous solution containing potassium bromide, potassium iodide and ammonia, and potassium bromide and potassium iodide aqueous solution it double jet method. Silver nitrate and halogen aqueous solutions were added at a constant rate of 20% of the total addition chamber (1st stage≦2nd stage-2nd stage-2nd stage) to form particles. Desalted by precipitation method to obtain an average particle size of 0. Tataμ,
Thickness 0.3 jpm, particle size/thickness ratio, 2. /J'I=tg
A morchi emulsion was obtained. This emulsion was used as a host grain in the same manner as in Example/-(5) (2 pAg adjustment, spectral dye 1j
After stirring for 70 minutes, a silver nitrate aqueous solution and a thorium chloride aqueous solution were added to grow epitaxial silver chloride in an amount of more than 1,000 mols. Epitaxy silver chloride is grown on the top of the tabular host grains in photosensitive emulsion E.
n1-1 was obtained.

An emulsion layer obtained by mixing this emulsion E m -■ with an internal fogging emulsion E m -H in a 3θ mold and a protective layer of an aqueous gelatin solution were separately and uniformly coated on a subbed polyester base, and dried to obtain a coated sample of 71610 tons. -Created nine. The amount of coated silver in the coated sample was /, Of/m2, and the amount of coated gelatin was 1.0% in the emulsion layer. evening? /m Protective layer θ,
rf/m.

(2) Measurement of developed silver amount Coated sample layers 7, 1 and 1 were exposed solidly under conditions that gave the highest density. Then, developer A (20°C/min,
It was developed for 2 minutes, stopped, fixed, washed with water, and then dried.

Table 1 shows the results of measuring the amount of developed silver for each sample C.

As is clear from Table 2, C'-, particle size/thickness ratio! The above coating sample /167 has a development rate of approximately /167 in %λ minutes.
In contrast to C2, which has a ratio of θθ, it cannot be said that the coated sample/16IO, in which the particle diameter/thickness ratio is less than that, is sufficiently developed even in the development of the damas.

Claims (1)

[Claims] A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support contains a light-sensitive silver halide emulsion and an internal bulky silver halide emulsion; The silver halide grains contained are tabular silver halide grains with a grain size of 5 times or more the grain thickness, and are hybrid grains in which a silver salt is epitaxially grown on the surface of the tabular silver halide grains. A silver halide photographic light-sensitive material.