JPS63235939A - Method for processing color developing - Google Patents

Abstract

PURPOSE:To simply obtain a color photosensitive material having the uniform property by incorporating an emulsion which has <=4mol.% of the mean silver iodide content in a silver halide and is composed from silver bromide, silver chlorobromide or silver chloride, in at least one layer of silver halide photosensitive layers. CONSTITUTION:The emulsion which has <=4mol.% of the mean silver iodide content in the silver halide and is composed of silver bromide, silver chlorobromide or silver chloride, is incorporated in the silver halide photosensitive layers. The color photosensitive material is processed in such way that the film surface of the silver halide photosensitive layer side is in contact with the stream of a processing solution having the flow speed different from the carrier speed of said color photosensitive material, without substantially exposing said material to a free air, in at least one step of color developing processings. Thus, the uniform finishing quality of the color photosensitive material is easily obtd. with rapid, simple and stable, even in the case of a simple processing.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention uses a silver halide color photosensitive material that has the ability to quickly display excellent color images, and can be easily processed quickly, easily, stably, and even in quiet processing. Uniform finish and high quality can be obtained,
This is about a compact color processing system.
In particular, the present invention relates to a color development processing method using a color photosensitive material having photographic sensitivity and using a prescribed processing liquid stream.

(Prior art) Conventionally, conventional color development processing, compared to the development processing of black and white light-sensitive materials, involves a desilvering step following color development, and this includes bleaching, bleach-fixing, or fixing. , a rinsing bath or a stabilizing bath is required, and the number of processing baths is large and the processing time is long. In the development process using the diffusion transfer method used in instant photography, the image-receiving layer is provided on a separate sheet, and after development, the light-sensitive material sheet is peeled off and removed. This substantially eliminates the desilvering process and speeds up the process. It's getting older.

Examples of common color development processing methods include a method in which color photosensitive materials are immersed in storage tanks for each processing solution under conditions such as predetermined temperature, time, and stirring; There are two methods: a method in which the photoresist is spread or coated on the photosensitive film surface of a color photosensitive material and developed, and a method in which a processing liquid of normal viscosity is brought into contact with the photoresist in a spray-like or film-like manner.

In addition, automatic developing devices include conventional hanging type developing machines,
Roller conveyance developing machine, automatic cine developing machine, rotary developing machine (
For example, there are automatic developing machines for disk film, rotating drum developing machines, and reel developing machines. In addition, a color development method for black-and-white light-sensitive materials, which requires only fixing and washing with water after development, is also convenient. For example, Itek's Venturi treatment, jet spray treatment, and Coder treatment (for example, U.S. Patent No. λ16
6r2 issue etc.) etc. PSdE magazine No.! Volume, Hiroshi
The process described in page A/year is known.

Immersion development processing of color photosensitive materials can be carried out with uniform and stable finishing quality. However, this requires a sufficient amount of processing liquid, a sufficient amount of replenishing liquid, and a relatively large storage tank. Many methods have been proposed to improve this defect, but all of them tend to increase the amount of liquid discharged, making the processing machine heavy and bulky. In addition, in order to avoid air oxidation fatigue due to contact of the processing solution with free air, for example,
There are measures to reduce the opening degree, such as No./-271r21.3. There are difficulties in removing the viscous liquid used in the development process using the viscous process liquid or in making each development process continuous. In addition, the method of developing by bringing the processing solution into contact with the film in the form of a spray or a web causes fatigue of the processing solution, especially the developer, and has problems in making the processing continuous and stable.

Particularly, in color photo labs, immersion development is performed, which is suitable for large-scale color development. When the amount of photosensitive dye to be processed suddenly decreases or when processing is slow, increase the amount of replenisher for processing to 5 times the normal amount and add a recovery liquid such as ``Revivi Ink Liquid'' manufactured by Fuji Film. We are working to restore the performance of liquids whose performance has deteriorated due to We are putting a lot of effort into its maintenance and maintenance.

As color photosensitive materials become more and more popular, there is a demand for rapid and simple color development processing, as well as compactness and easy maintenance of color development processing machines or systems including printing processes.

Regular color photographic paper provides excellent image quality in 2- or 3-bath processing in about 3 minutes and seconds, and color reversal paper can be processed in a minilab in about 1 hour.

The development process has been completed. However, these photographic papers cannot be used for photography due to their extremely low sensitivity. Minilab processors are also required to be more compact than simple copier processors, and the processing time is also required to be approximately 10 seconds or less, preferably 120 seconds or less. Instant photography is a type of photographic material, and has formed a field due to its high sensitivity and quick and easy processing. However, the format is fixed, making it difficult to print multiple copies at the same time, and there is still room for improvement in terms of image quality and price. Although the color negative light-sensitive material is much faster than Kodak's C-≠l processing, it still takes 77 minutes and 20 seconds, and by integrating the bleaching and fixing functions, the bleach-fixing process can also be performed at 3R 0C and 11 lose one's time Even if patch-type development processing is performed forcefully for about 10 minutes, continuous processing cannot be achieved. Even if Niji rapid desilvering process is adopted in the minilab, continuous processing will result in l1 at 31r0C.
It takes 30 minutes. On the other hand, in the market where a desired number of prints of excellent image quality can be obtained at a reasonably low cost, the color negative/positive system is a quick and simple continuous color development process that allows prints to be obtained anywhere, anytime. desired. For this purpose, it is necessary to develop a quick and simple color development processing method that takes advantage of the excellent image quality such as color reproducibility, image sharpness, and graininess, and high sensitivity of color negative light-sensitive materials.

Currently, DIR couplers (couplers that react with the oxidized product of a color developing agent and release a development inhibitor) are used in all color negative light-sensitive materials on the market in order to obtain high image quality. DIR couplers are also known to retard color development. Furthermore, in order to provide high sensitivity, suppress fog, and control the progress of development, it is common to use a photosensitive silver halide emulsion containing more than μmole of silver iodide.

As for color negative photosensitive materials, the color development processing time is longer than that of color photographic paper, and it is considered extremely difficult to provide high sensitivity and rapid processing characteristics while maintaining high image quality. The color development processing time is preferably 1 to 2 minutes (excluding drying time), and as a color negative/positive system, it is preferably within 2θ minutes, preferably within 13 minutes. has been done. In order to overcome these conventional deficiencies and meet the demands, it is first possible to improve the color photosensitive materials and the color development processing systems used.

A seventh object of the present invention is to provide a new, compact color development processing system that can easily provide uniform performance even during idle processing, with less fatigue of the processing solution and easy maintenance. Second, the color development processing time is about 1 minute,
The objective is to provide color photosensitive materials that can be used in the new color development processing system. Other objectives will be apparent from the description herein.

The inventors made a number of prototype color light-sensitive materials and examined their compatibility with developing systems, and were able to achieve the object of the present invention in the following manner.

A color photosensitive material is used in which a silver halide photosensitive layer containing a yellow coupler, a silver halide photosensitive layer containing a magenta color photographic paper, and a silver halide photosensitive layer containing a cyan coupler are provided on a support. image exposure,
In a color development processing method including color development and/or simultaneous desilvering processing, at least one layer of the silver halide photosensitive layer group contains silver halide having an average silver iodide content of V molar ratio or less;
Using an emulsion consisting of silver bromide, silver chlorobromide or silver chloride,
and at least one step of the color development process is performed without exposing the color photosensitive material to a processing solution stream having a flow rate different from the conveyance speed of the color photosensitive material to substantially free air. A color development processing method characterized in that the processing is carried out by contacting the film surface on the layer side.

The specific photographic sensitivity of a light-sensitive material as used in the present invention is determined according to the following test method based on ISO sensitivity.

According to JIS K 7A/4 (-15#/).

A first feature of the present invention is the use of a system that includes color development processing using a processing liquid stream. Color development processing using a processing liquid stream refers to ``color development processing in which a stream of processing liquid produced at a flow rate different from the transport speed of the color photosensitive material is brought into contact with the photosensitive film of the color photosensitive material in a limited space. "method". In order to smoothly perform continuous rapid processing, the color photosensitive material is preferably processed while being continuously conveyed in a limited space. The direction of the processing liquid stream is preferably the same as the direction of transport of the color photosensitive material in order to start processing with a new processing liquid introduced and to reduce the amount of processing liquid. The flow rate of the processing liquid stream may be different from the conveyance rate of the sensitive material to be processed, and preferably the relative speed may be controlled such that laminar flow also substantially causes turbulence. By taking advantage of this, it is possible to process extremely evenly and stably. The process solution (IJ-me) is designed to be isolated from free air in order to keep the capacity of the process solution stable and only require a small amount.

Here, in the color development process using a processing liquid stream, a limited space means a developing machine that is cut off from free air, and is a developing machine that satisfies the shaded area shown in FIG. q.

Therefore, conventionally known laminar flow development has a large interface with air and is outside the scope of the automatic processor of the present invention.

As the term suggests, laminar flow development is development in which a processing stream flows gently over the sensitive material as a laminar flow due to the force of gravity, and is completely different from the color development process using a processing liquid stream as used in the present invention. That is, in this process, the photosensitive material moves between the narrow slits described above, and the processing liquid is supplied at a speed different from the movement, and processing is performed in a substantially turbulent state.

FIG.

In the figure, A, B, C, and D are commercially available general processors E, F is a special processor such as a minilab, and Y is a processor shown in Example-C and Example-1 of the present invention. shows.

In X1Y, the tank liquid capacity is extremely small and the opening degree is extremely small.

This is the tank opening degree. means.

Development using a processing liquid stream in the present invention often starts with a newly supplied processing liquid, so although it is a continuous process, the performance of the newly supplied processing liquid can be maintained and stabilized. The process progresses and the processing time is shortened. By reducing the cross-sectional area of the limited space and controlling the relative transport speed of the processing liquid stream and the color photosensitive material in accordance with the processing time of the processing liquid, extremely efficient processing can be achieved, reducing the amount of liquid discharged. Instead, it can reduce the amount of recovery fluid and replenishment fluid.

Furthermore, even when continuous processing is interrupted and a very small amount of color photosensitive material is processed intermittently, it is possible to easily obtain stable finishing quality. Since the treated liquid can be continuously collected in bulk, the treated liquid can be regenerated efficiently.

Therefore, by applying the color development process using the processing liquid stream according to the present invention, a compact, quick and easy color development process system can be created.

In treatment with a treatment liquid stream, the surface of the member creating the confined space may be provided with a treatment liquid impregnated polymeric sheet material, preferably movable. It is convenient for removing scum from processing liquid and stably supplying a small amount of processing liquid.

The next feature of the present invention is a color photosensitive material that is suitable for rapid and simple processing. The factors that hinder the rapid and simple color development process are, firstly, the halogen composition of the silver halide grains, and secondly, the silver halide adsorption type heterocyclization used in fog suppressants, stabilizers, etc. Thirdly, the DIR compound.Furthermore, regarding the desilvering process, firstly, the sensitizing dye used in the halogen composition tube 2 of silver halide, thirdly the DIR compound.
Examples include the presence of an IR compound, a silver halide, or an adsorbed heterocyclic adduct of silver.

First, in the silver halide emulsion used, especially its halogen composition, the silver iodide content should be reduced to an extent that does not substantially inhibit the desilvering effect of color development, or silver iodide should not be included. The method is to use silver bromide, silver chlorobromide, or silver chloride. Silver chlorobromide or silver chloride is preferred because silver bromide and silver iodide also have a slight effect of inhibiting color development. The content of AgI depends on the type of development inhibitor used,
Although it depends on the type of antifoggant and stabilizer and the amount used, it is preferably about J molti, more preferably about λ molti or less, and more preferably 1 molti.
If possible, it should not contain substantially less than the molar ratio.

In order to obtain high sensitivity with an emulsion having a low silver iodide content, an improved method for forming silver halide grains may be used in combination with techniques for overall improvement of image sharpness and graininess similar to those described above.

Currently, there are no color negative photosensitive materials for photography or color reversal photosensitive materials that use a silver iodide emulsion containing approximately λ mol% iJ, preferably less than 1 mol, or substantially no silver iodide. do not have. This is because silver halide emulsions for high-sensitivity negative types generally use silver iodobromide emulsions, and silver halide emulsions for low-sensitivity photographic paper use silver chlorobromide or silver chloride emulsions. It is. For example, Mei Kikuchi, Photo Chemistry, Kyoritsu Shuppan (Showa Geta), Chapter 1, 17-
Description on page 1 of Photographic Chemistry Volume 1 by Pierre Glafkides, published by Fountain Press (2013), Chapters 1 to 20, 327 to 36? Page descriptions, especially Chapter 3 of the Japan Photographic Society Network, Basics of Photographic Engineering, Ginshishamei Edition, Coronasha Publishing (Showa to 2010), 1995, /.

This is clear from the description in Section 2, pages 103 to 1017.

The highly sensitive silver halide emulsion according to the present invention is approximately
Silver iodobromide emulsions, silver iodochlorobromide emulsions, preferably silver bromide emulsions, silver chlorobromide emulsions, etc., containing silver iodide of less than 2 mol sH, preferably less than 2 mol sH. In order to obtain high sensitivity, many defects are added to the crystal lattice during the grain formation process, such as grains with many twin planes, multi-structured grains and grains created by changing pAg or halogen composition during the grain formation process. Particles in which the direction of crystal growth is changed by adding substances adsorbed to other silver halides in the process, and in the process of crystal formation, different metal ion complexes or salts such as lead chloride, iridium chloride complexes, salts, compound complexes, etc. Silver halide grains to which palladium chloride complexes, rhodium chloride complexes, etc. have been added, and compounds that become silver halide solvents during the crystal formation process, especially in the later stages, such as thiocyanates, thioether compounds, and hyponaline, are added to etching the surface. particles with irregular growth, particles with different crystals bonded by epitaxial bonding, particles with high silver iodide sensitivity crystal bonded to a low silver iodide crystal substrate,
Particles with roughened surfaces to increase surface area, particles with multiple chemical sensitizations applied during the particle formation process, and particles with sensitizing dyes adsorbed during the crystal growth process or before chemical sensitization to achieve spectral enhancement. Preferably used are sensitized particles, or particles in which rainbow-sensitized nuclei are concentrated and strengthened by selectively using a small amount of a chemical sensitizer.

Highly sensitive silver halide emulsions according to the present invention can be obtained by selecting from these various silver halide grains and chemically sensitizing them appropriately in accordance with the characteristics of the silver halide grains.

The diameter of silver halide grains is about 0.2μ! μ is used. For example, British patent no.

No. 27/G, No. 2031'7 Octopus, U.S. Patent No. 3
torotr issue, same number 4<+44ef77, same number 4I
oylItrq No. 111172700, No. 1
3/3 issue from Ig, same issue ≠ 3tt26λ, same issue 11
No. 3911778', same No. 4Z, 4A, 33, 1
0/No. 1111A30r7, No. 3tjtYt
No. 2, No. 3112067, Tokukai Sho! F-7A J4
tO issue, Douaki! l-10r126, Showa 11-///
Ri3! No., Douaki! 1-///ri No. 3, Dosho! r-//
/ri No. 37, special request! The basic technology is suggested in the descriptions such as No. I-+211141. LF if necessary)
A small grain emulsion of 0.2 μm or less can be mixed and used. A method for producing such an emulsion is described in U.S. Patent No. 3. ! 7 da,
No. 621, 3°Ar 1,32g and British Patent No. 1,1713°74tr. Also, JP-A-Sho ur-rtoo, t/-39027, t/-39027, j/
-130ri No. 7, 13-/37/33, same jμm≠
112/issue, same! Dar 271/2, same! t-37t3
! Monodisperse emulsions such as those described in No. JR-1 Tag No. 3R, etc., can also be preferably used in the present invention.

Tabular grains having aspect ratios of about 3 or greater are also useful in the present invention. Tabular grains are described in Photographic Science and Engineering by Gutoff.

Photographic 5science an
dEngineering) + Volume 11, 211r ~
2j7 page (70 years): U.S. Patent No. 4', eJ≠, Ko λ, 4Z, 4t/g, JlO, 173
3.

l 7- oIIr No., same≠,≠32. ! No. 20 and British Patent No. 2. It can be easily prepared by the method described in, for example, No. //2,167. When using tabular grains, there are advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as disclosed in the above-cited U.S. Patent No. 1.4 (J≠, λ2 is described in detail in the issue.

The silver halide emulsion according to the present invention can be produced by controlling I) Ag in the liquid phase in which silver halide grains are generated and grown, and by controlling temperature and stirring in a predetermined pattern, and by controlling halogens such as sodium chloride, potassium bromide, and potassium iodide. It is manufactured using a double-jet emulsion manufacturing device that controls the addition of silver nitrate and silver nitrate.

In the production of the silver halide emulsion used in the present invention, compounds described in Research Disclosure, /774', /17/l are used. The diameter of silver halide grains is 0
, 0/-0, micro-μ fine grain emulsion can also be used for the protective layer and intermediate layer.

When the iodine content of the silver halide emulsion is low, particularly when it is less than 2 molar, the light absorption/absorption in the blue wavelength region decreases, and sensitivity in the blue wavelength region is likely to be insufficient.

In order to compensate for the lack of sensitivity caused by this decrease in light absorption, the particle size/surface area ratio is small, and a diameter/thickness ratio that allows addition of a large amount of sensitizing dye for short-wave sensitization and increases light absorption is required. In the present invention, it is preferable to use tabular grain sounds of 5 or more.

In addition, silver halide grains include regular grains with regular crystal bodies such as cubes, octahedrons, and dodecahedrons, but when the iodine content is low, the number of crystal defects decreases, resulting in a decrease in sensitivity. occurs.

Therefore, it is preferable to intentionally introduce all crystal defects into the emulsion used in the present invention. Preferably used are grains in which a silver halide adsorbent material, a foreign halogen, and a foreign metal ion are all added in the process of grain formation to completely introduce crystal defects.

Particularly preferred for the present invention are emulsions containing silver halide grains in which development is initiated from singular points of the silver halide grains or, for example, from the apexes or edges of the crystals. For example, Tokkun Sho 4/-3/
The vertices of cubes with (lOO) facets and /ghedral particles described in issue //3/ etc. or limited (///
) and the apex developing particles (CDG) that start development on the (/
CDG emulsions have predominantly apex developed grains of t-hedral grains with //) faces, or edge developed grains of tabular grains (EDG).
Preference is given to EDG emulsions having predominantly J. These C
DG emulsions and EDG emulsions have the same silver halide composition but are extremely advantageous for rapid and simple processing compared to grains in which the development center is not controlled. It can be sensitized and has good stability over time. It is also preferable to use a CDG emulsion or an EDG emulsion for a color photographic material having a silver halide emulsion layer containing a higher silver chloride content and a lower silver iodide content than conventional ones or no silver iodide content in the production of color photographic paper. In order to produce CDG emulsions and EDG emulsions, a multi-structure grain manufacturing method is used, in which a halogen conversion initiation inhibitor (CR compound) is used in the grain formation process. For example, Tokugan Showa t/-J///J/
It is written in the number etc.

CR compound is also a conversion initiation inhibitor that selectively adsorbs (100) plane or (///) plane and achieves an adsorption state, but for <1oo) plane, most of them are expressed by the general formula (1), [
sensitizing dyes according to II) or [■], sensitizing dyes with their J aggregates especially on the (II/) plane, or adsorbed heterocyclic compounds on the crystal plane of silver halide, such as general formula [■] ], [■'] or compounds of (V) are particularly preferred.

It can be said that the CR compound adsorbs to crystal planes where there are few development centers, so that it has little inhibiting effect on rapid and simple development. Furthermore, if the CR compound is endowed with a spectral sensitization function, a fog prevention function, and a stabilizing function against photosensitivity and fog, all of the above-mentioned functions can be imparted without inhibiting rapid and simple processing. This is a surprising beneficial effect.

Here, the CDG emulsion means that the silver halide crystals in the emulsion are at least substantially (ioo cubic or/
It is a trihedron or a t-hedron with (///) faces, and the (maximum density - minimum density) of the silver image in the characteristic curve of the emulsion obtained depending on the developer and development temperature used to process the photosensitive material. Exposure was carried out for 1710 seconds under exposure conditions corresponding to 2 l - ×3/da, and after development was started, immediately after the exposure of glacial acetic acid! At least 70' of the number of silver halide crystals (grains) processed and developed under the same conditions as above except that they were stopped with an aqueous solution.
If la is the vertex of the edge or its vicinity and / is a monohedron, & is (
/ / /) refers to a controlled emulsion that is developed on the surface. More specifically, for example, the following method can be used as a guide for discrimination.

That is, a silver halide emulsion is deposited on a support at a silver content of O1! ~3
Apply t/rrL2 and develop at 3o'C using the following developer.
171 under exposure conditions corresponding to (maximum density - minimum density) x 3/g of the silver image in the characteristic curve obtained by developing with
After 0 seconds of uniform exposure and development with the same developer at 300C for 10 seconds, the development was stopped with an aqueous solution of glacial acetic acid.

In this case, cube or l≠hedron or? Silver halogenide grains which are developed at or near the apex of the edge of a hedron and on the (///) face in the case of a monohedron are referred to as vertex-developable grains (CDG).

-,2,2- Here, to determine whether or not the silver halide has been developed, it can be done by separating the silver halide grains according to a conventional method and observing the blackened developed silver with an electron microscope.

The details of this method will be described in Experiment (1).

Also, of the number of particles developed in this way, at least 70% of them are further
In the case of a face piece, when the emulsion is developed on the (///) face, the emulsion corresponds to the CDG emulsion of the present invention.

The ratio of the number of particles is calculated by observing 200 developed silver particles under an electron microscope.

Here, "near the apex" preferably means that one side has a length of about 1/3 of the diameter of a circle with the same area as the area of the projected cube, llI-hedron particle, or r-hedron particle, and the apex is one of the sides. It means within the area of a square with two corners.

Also, preferably at least 70% of the number of particles developed in this way have an aspect ratio of 5 or more! ~
When the tabular grains of CoO are developed at or near their edges, the emulsion corresponds to the EDG emulsion of the present invention. In addition, the term "near the edge" as used herein means that the area is preferably within a distance of -side from the edge, with one side having a length of about 1/3 of the diameter of a circle having the same area as the projected tabular grain. do.

(Developer composition) ・Triethanolamine tCc・
N,N-diethylhydroxylamine (rr water solution) jcc・ethylenediamine≠acetic acid・JNa・2H202,2?・N-Ethyl-N-(β-methanesulfonamidoethyl)-3 monomethyl-guaminoaniline sulfate z, of・Sodium sulfite 0. /3?・Nact
/,≠2・Potassium hydrogen carbonate! t.potassium carbonate
ivy water upto 10OO
CC pH=/a, 10 In the method for determining CDG emulsion or EDG emulsion described above, a silver halide emulsion is exposed to light for 17100 seconds, developed under the above conditions, and then stopped to determine the developed silver halide emulsion. Of the particles, at least 70 tO
It is preferable that the edges are developed at or near the vertices of the edges of the cube, lg-hedron, or t-hedron.

The monodisperse emulsion according to the present invention is an emulsion having a grain size distribution in which the coefficient of variation (S/r) regarding the grain size of silver halide grains is 0°2j or less. Here, r is the average particle size and S is the standard deviation regarding the particle size.

That is, when the grain size of each emulsion grain is ri and the number of emulsion grains is ni, the average grain size r is defined as Σn1-ri r = Σni, and its standard deviation S is defined as -+2 j − .

Next, preferred CR compounds will be explained.

In the formula, z101 and Z102 each represent an atomic group necessary to form a heterocyclic nucleus.

Examples of the heterocyclic nucleus include a j-A membered ring nucleus containing a nitrogen atom and other heteroatoms, such as a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom (a fused ring may be further bonded to these rings). , or further substituents may be bonded)
is preferred.

Specific examples of the above heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, -26 = selenazole nucleus, benzoselenazole nucleus, nandoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, imidazole. Nucleus, benzimidazole nucleus, naphthoimidazole nucleus, Hiro-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tellazole nucleus, penzotelllazole nucleus, naphthotellazole nucleus, etc. I can name a tiger.

RIOI and 1102 each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group.

These groups and the groups described below are used to include their substituents. For example, taking an alkyl group as an example, it includes unsubstituted and substituted alkyl groups, and these groups may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably / to r.

Specific examples of substituents for substituted alkyl groups include halogen atoms, cyano groups, alkoxy groups, substituted or unsubstituted amine groups, carboxylic acid groups, sulfonic acid groups, hydroxyl groups, etc. or a combination of two or more may be substituted.

A specific example of the alkenyl group is a vinylmethyl group.

Specific examples of the aralkyl group include benzyl group and phenethyl group.

m101 represents a positive number such as O, l, λ, or 3.

When m 101 represents /, R103 is a hydrogen atom,
Represents a lower alkyl group, an aralkyl group, or an aryl group.

Specific examples of the aryl group include substituted or unsubstituted phenyl groups.

R104 represents a hydrogen atom. When mlO□ represents 2 or 3, R1 (13 represents a hydrogen atom and R104 represents a hydrogen atom, a lower alkyl group, an aralkyl group, or can be linked with R102 to form a j-membered ring) In addition, when m1o1 represents 2 or 3 and R104 represents a hydrogen atom, R103 may be linked with another R103 to form a hydrocarbon ring or a heterocycle. Preferred. jlol, ktot represent O or l, X 101 represents an acid anion, n1
01 represents O or l.

General formula (II) In the formula, Z201, Z202Jd, the above Z 101 or Z
It is synonymous with 102. R201 and R2O2 are RIOI or R102 and F[de')') R2O3 represents an alkyl, alkenyl, alkynyl or aryl group.

m201 is 0. / or ko. R204 represents a hydrogen atom, a lower alkyl group, an aryl group, and m 2
When 01 represents 2, R204 and R204 may be connected to form a hydrocarbon ring or a heterocycle. These rings! ~6-membered rings are preferred.

Q201 is a sulfur atom, an oxygen atom, a selenium atom or >N
It represents R2O5, and R2O5 has the same meaning as R203.

j 201, R201, X201 and n201 are husband kjxot.

k engineering. 1, Xl0I and n□. Represents the same meaning as 1.

General formula [111] In the formula, Z 301 represents an atomic group necessary to form a heterocycle. Examples of this heterocycle include those mentioned in relation to Z 101 and Z102, and other specific examples thereof such as thiazolidine, thiazoline, benzothiazoline, naphthothiazoline, selenazolidine, selenazoline, benzoselenazoline, naphthothiazoline, benzoxazoline, naphthoxazoline, dihydropyridine, dihydroquinoline,
Examples include benzimidacillin and naphthymidacillin. Q301 is synonymous with Q201. R
301 is R101 or R102, R302 is R2
〇m 301, which is synonymous with O3, represents the same meaning as m 201. R303 has the same meaning as R204, and when m 3ot represents 2 or 3, R303 and another R303 may be linked to form a hydrocarbon ring or a heterocycle. j a
ol represents the same meaning as j101.

Next, specific examples of sensitizing dyes used in the present invention will be given. However, it is not limited to this.

What is important for the present invention is that if the bromide ions used for conversion are supplied at a high concentration, the conversion proceeds very rapidly.
The functionality of the compound will be relatively reduced.

Therefore, it is preferable to slowly supply bromine ions at a relatively low concentration. In the presence of a CR compound, when conversion is initiated at or near the apex, e.g. (10
0) Is it possible to progress to the center of the surface and eventually convert the entire surface? Jru. The new converted surface has almost no change in appearance, with only slight groove-like or ring-like defects occasionally being observed on the apex or surface of the particle. The halogen ions necessary for conversion may be supplied by, for example, a water-soluble bromide such as potassium bromide, but a donor whose supply amount or rate of bromide ions can be controlled is preferable.

For example, an organic halogen compound, an inorganic halogen compound having appropriate solubility in water, a halogen compound whose capsule membrane is covered with a semi-permeable film, etc. can be used. Practically speaking, it is preferable to use silver halide which is finer than the host grains and has a higher silver bromide content than the host silver halide. For example, in an emulsion containing host silver chloride grains to which the OCR compound has been adsorbed, the average grain size corresponding to about 1 molar portion of host silver chloride is about 0. When an emulsion containing fine silver bromide grains of /μ is mixed and ripened to cause conversion, the silver bromide grains dissolve and disappear, and after reaching equilibrium, a new layer of nitrogen composition is formed on the surface of the host grains. is formed and the reaction stops. The surface that is formed at this time has a composition resulting from the precipitation of a silver bromide-rich phase and the homogenization of the nitrogen composition that occurs in parallel, and the amount of silver bromide on the surface is only about 3 molt. had not been reached. Probably during the conversion process.
It is thought that at least silver chloride and silver bromide are mixed by repeated dissolution and recrystallization, and that silver bromide is diffused to some extent inside the grains.

The silver halide composition of the surface in the present invention is determined by XPS (x-
ray Photoelectron 5pectro
Shimadzu-duPont ESC using the Scopy method
It can be observed using an A7so type spectrometer.

Measurement of silver halide composition by the XPS method is described in "Surface Analysis" co-authored by Someno and Yasumori, published by Kodansha (published in 1977).

The above-mentioned "surface" can be considered to be within about 10 grids as a guideline, according to the figure i3 of the above-mentioned "Surface Analysis" on page 3.

It can be seen that when a CR compound is adsorbed to the host silver halide grains according to the present invention and halogen conversion is performed using fine grain silver halide grains, the development initiation point is controlled and concentrated at or near the apex.

The same can be said of CR-compounds for (///) planes and t-hedral crystals and tabular grains having (///) planes. Particularly preferable CR-compounds for the (///) surface are sensitizing dyes that adsorb in the <KJ aggregate state in the compounds represented by the general formula [I], [I[) or [■], Compounds represented by the following general formulas [■] and [■] are preferred.

General formula [■] In the formula, Zl represents an atomic group necessary to form a saturated or unsaturated heterocycle with the sulfur atom, and this heterocycle may have a substituent.

Here, the atomic group represented by Zl is formed from a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and the heterocycle formed from Zl and a sulfur atom is a 3- to r-membered heterocycle; It may be fused with another ring to form a fused ring.

Specifically, thiirane, chetane, thiane, chepin, thiosine, dihydrothiolane, thiophene, dihydrothiobilane, ≠H-thiobilane, JH-thiobilane, /, 3
-thiacyridine, thiazole, /, 3-oxathiolane, /, 3-dithiolane, /, 3-dithiolane, /, 3-
Dithiolane, /.

Examples include ≠-oxathiane, l, ≠-thiazane, /, J-thiazane, benzothiolane, benzothiane, benzothiasilidine, penzosaxathiane, and the like.

As a substituent of a heterocycle formed from Zl and a sulfur atom,
Specifically, a carbon atom, an alkyl group (preferably one with carbon number/-20), an aryl group (preferably one with carbon number t)
-20), alkoxy group (preferably carbon number J-
20), aryloxy group, alkylthio group, arylthio group.

Acyloxy group, amine group, carbonamide group, ureido group, carboxy group, carbonate ester group, oxycarbonyl group, carbamoyl group, acyl group, sulfo group, sulfonyl group, sulfinyl group, sulfonamide group, sulfamoyl group, cyan group, hydroxy group, nitro group, oxo group, thioxo group, imino group, and selenoxo group.

When there are two or more substituents, they may be the same or different.

Further, among the compounds represented by the general formula [IV], preferred ones can be represented by the following general formula [■'].

General formula [■'] In the formula, Z2 is a sulfur atom and a carbonyl group! ~-Hiro l
- represents an atomic group necessary to form a saturated or unsaturated heterocycle, and this heterocycle may have a substituent. Here, the atomic group represented by Z2 and the substituent of the heterocyclic ring formed from Z2, a sulfur atom, and a carbonyl group are the substituents of the heterocyclic ring formed from Zl and Zl and a sulfur atom represented by the above general formula CIVI). means the same thing as

n represents 1-3. When n is 2 or 3, each carbonyl group may be adjacent or non-adjacent.

Represented by the general formula [■′]! Specific examples of the saturated or unsaturated heterocycle in which ~ is a member include the following. Particularly specific examples include the compounds described in the specification of Japanese Patent Application No. 1987-1-It'll-2.

Among those represented by the general formula [■'], particularly preferred are those in which the carbonyl group is linked to a sulfur atom, and the heterocycle is saturated.

Specific examples of the compound of the present invention represented by the general formula [■'] are shown below.

IV'-(1) IV'-(2) IV'-(3) IV'-(51 Furthermore, the same thing happens to the edges of tabular grains in EDG emulsions. In other words, in the grain formation process, ( ///) For multi-structure particles using a CR compound for the C
By using the R compound, development centers are concentrated at or near the edges, making it possible to speed up the development. A particularly preferred CR compound is a compound represented by the following general formula [v].

General formula (V) R1-8-(X)m-Y-R2 X is a divalent shoulder group, alkylene, arylene, alkenylene, -5O2-1-SO-110-1-S- 1
-C-1-N- alone or in combination. Alkylene, arylene, and alkenylene may have a substituent. The substituents are the same as those listed for R1.

R3 is a hydrogen atom, an alkyl group, or an aryl group.

m is O or l.

R1 represents a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

Preferred examples of Ro include a hydrogen atom and a substituted or unsubstituted alkyl group. Substituents include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, sulfonyl groups, sulfonamide groups, amide groups, acyl groups, sulfamoyl groups, carbamoyl groups, ureido groups, alkoxycarbonylamino groups, and allyloxy groups. Carbonylamino group, alkoxycarmenyl group, aryloxycarbonyl group, aminocarbonylthio group, alkylcarbonylthio group, arylcarbonylthio group, cyano group, hydroxy≠! - Examples include a cy group, a mercapto group, a carboxy group, a sulfo group, a nitro group, an amine group, an alkylthio group, an arylthio group, and a heterocyclic group.

R2 represents a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amine group, an alkoxy group, or an aryloxy group. As a substituent, R
Something similar to 1 is possible. Preferred examples of R2 include a hydroxy group, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted amine group.

Y represents -CO or -8O3, preferably -C
It is O.

The total number of carbon atoms including the substituents of the organic groups of X, R1, R2, or R3 is preferably 20 or less, respectively.

Specific examples of the compound represented by the general formula [v] used in the present invention are shown below, but the scope of the present invention is not limited to these compounds. Specific examples of this CR-compound are described on pages 10 to 1 of the specification of Japanese Patent Application Sho A/-/l'A≠r1-≠6-.

In the CDG emulsion or EDG emulsion according to the present invention, the latent image or development center is concentrated and extremely high sensitivity is achieved, and the main (lOO) plane or (///) plane has a new silver halide structure due to conversion. Alternatively, since the film is protected by a multilayered structure formed by the growth of particles, the stability is significantly improved, and it is possible to promote rapid developability, suppress fogging, and obtain excellent stability over time. Surprisingly, a high-contrast emulsion can be obtained, and since it has excellent pressure resistance, it has the advantage of less pressure desensitization and less fog in unexposed areas.

The CR compound according to the invention has the characteristic that it can be selected from among sensitizing dyes. CR is especially useful for (10O) planes.
The compound can be selected from the compounds represented by the general formula CI), (nettake [■]), and (///
) The J-aggregate type compound is particularly good for the surface, and can also function as a sensitizing dye, so it is advantageous for increasing the spectral sensitivity, and in particular, it is possible to further stabilize the spectral sensitivity by conversion. can.

The discovery of such an excellent combination and its effects is surprising.

Furthermore, in order to increase sensitivity and stability, it may be combined with other sensitizing dyes, or may be used in combination with a supersensitizer.

For example, a substituted aminostilbenzene compound with a nitrogen-containing heterocyclic ring group (e.g., patent application Showa A/-JJ filed by Fuji Photo Film on February 30, 1999)
The compounds of general formula (I) described in /≠R specification, particularly specific compound examples (I-/) to (I-/7), and U.S. Patent No. 2. 33.320, same! , 13! , 7 pieces/
(as described in US Pat. No. 3,7173,610), aromatic organic formaldehyde condensates (such as those described in US Pat. No. 3,7173,610), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3. t/j, t/3, same J, A
I! , l≠/issue, same J, t/7゜kota! No. 3, 13
The combinations described in Jt, No. 72/ are particularly useful.

The color coupler used in this invention has a high Those that have activity and are suitable for rapid processing are preferred.

For example, as a magenta coupler! - Pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (such as benzoylacetanilide,
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a pallast group in their molecules, or are polymerized. The coupler may be either ≠ equivalent or 2-equivalent to silver ions, but in order to reduce the silver content in the photosensitive material, a 2-equivalent coupler with higher silver utilization efficiency is recommended. It is preferable to use

In particular, when the same photosensitive emulsion layer is composed of two or more emulsion layers with different sensitivities, the most sensitive emulsion layer of each of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer has a 2-equivalent emulsion layer. It is preferable to include a coupler.

-! O- Also, as the coupler used in the present invention, a so-called fast reaction coupler having high coupling reactivity can be used.

The coupling reactivity of couplers is determined by the color image obtained by mixing two types of couplers M and N, which give different dyes that can be clearly separated from each other, and adding the mixture to an emulsion for color development. It can be determined as a relative value by measuring the amount of pigment.

The maximum concentration of coupler M (DM) max,, in the middle stage, the color development of the concentration DM, and the color development of coupler N, (DN)may,, if we express the color development of DN, then the ratio of the reaction activity of the two-power puller. RM/RN is expressed by the following formula.

In other words, various -j/
The coupling activity ratio RM/RN can be determined from the slope of the straight line obtained by plotting several pieces obtained by applying exposure to light in the - stage and color development.

Here, by determining the RM/RNO value for various couplers as described above using a fixed coupler N, the coupling reactivity can be determined relatively. Turnip Sea N above
For example, use the coupler below to find it.

α for cyan coupler α − for magenta coupler and yellow coupler
! The fast-reacting couplers used in the present invention have an RM/RNO value of 1.5 or more for cyan couplers, 2.3 or more for magenta couplers, and 1 for yellow couplers. It is preferable to have a value exceeding .

Specific examples of fast reaction couplers preferred for use in the present invention are shown below, but the present invention is not limited thereto.

Example of cyan coupler (CYAN-/) (CYAN-ko) One! 3- (CYAN-j) (J 1.2) (CYAN-4) (CYAN-j) (,2,7) -yo ≠- (CYAN-A) Example of magenta coupler (MAGENTA-/) (MAGENTA- ,2) α (/g) (MAGENTA-3) (MAGENTA-≠) α (7,≠) (MAGENTA-4) One! 7- (MAGENTA-t) (MAGENTA-7) 4r- (MAGENTA-f) (MAGENTA-ta) (MAGENTA-10) (7,7) (MAGENTA-1/) Example of yellow coupler (YELLOW-/) ( YELLOW-,2) -A/- (YELLOW-,?) (YELLOW-4) t2- (YELLOW-j) CH3 In the present invention, such a fast-responsive coupler is at least the most sensitive of each color-sensitive layer. It is preferable to add it to the unit emulsion layer. There is no particular restriction on the amount used, but silver 1 mole cyanide fast reaction couplers o, ooz
~0. /, magenta fast reaction coupler o, oor~o
, i, yellow fast-reacting coupler 0.00j-0,/ is preferred.

In addition, the present invention is based on paragraphs 1 and 3 to r of U.S. Pat. Tar l
By using a diffusion-resistant coupler in which the generated dye has moderate diffusivity, as specified in No. 103A, it is possible to improve sensitivity and graininess by increasing covering power. . These couplers are disclosed in the above-mentioned patents, as well as in JP-A-74-1931, JP-A-17-3931A, JP-A-101226, and U.S. Patent No. t, 26≠1723.
It can be easily synthesized according to the method described in No.

Specifically, the special application No. 7/1970-20/7jt,! Examples include those listed on page 1 to page zr.

The DIR compound or coupler used in the present invention is used in an amount that does not substantially inhibit or inhibit color development. In the present invention, it is particularly preferable to use a DIR compound selected from the group of compounds represented by the general formula (Vl) or [■] in the middle method of DIR compounds.

General formula (Vl) General formula [■] A-(LX) “Z2-C(L2).-Y) b formula chunin reacts with color coupler residues and oxidized forms of crude drugs and separates to form coloring pigments For example, U.S. Pat.
Residues described in -6μ Octopus No. 7, JP-A-Shojλ-/l/237, etc. are used.

As the color coupler residue, the following ts- can be used. Yellow color coupler residues represented by A are piparoylacetanilide type, dunzoylacetanilide type, malondiester type, malondiamine type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type, benzothiazolylacetate type. type, benzoxacylylacetamide type, benzoxacylylacetate type, benzimidazolylacetamide type or benzimidazoyl acetate type, and U.S. Patent No. 3゜rμ/
, rro, a coupler residue derived from a petro ring-substituted acetamide or a petro ring-substituted acetate, or U.S. Pat. No. 3,770, ≠≠6, British Patent No. 1
．． ≠! No. 777, West German Patent (OLS) No. 2. jtO
J, 0 Tata No., Japanese Published Patent No. 60-/3, 73j
or Research Disclosure No. 11737, or U.S. Patent Nos. ≠, O≠7, t7! The heterocyclic-substituted coupler residues described in the above are preferred.

Examples of magenta color coupler residues represented by A include oxo λ-pyrazoline nucleus, pyrazolo-[/, za
: ] Coupler residues having a benzimidazole nucleus, a cyanoacetophenone type coupler residue or a pyrazolotriazole nucleus are preferred.

The cyan color coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus.

Furthermore, after the coupler residue represented by A couples with the oxidized form of the developing agent and releases a development-inhibiting sidetone, substantially no dye formation may occur. Coupler residues of this type represented by A include U.S. Pat.
Same No. ≠, orza, lli No. 1, same No. 3. t, 32.3gj
No. 3. Rijt, No. 223 or No. 3 of the same. Coupler residues described in No. 6/, No. 6 and No. 6 are mentioned.

A reacts with the oxidized product of the color developing agent to form -Z2-
C(L2)il-Y)5 residues are all releasing coupler residues.

Ll is a timing group, and a represents O or all l.

Examples of the linking group represented by Ll include those shown below.

-0CR2- (linking group described in U.S. Patent No. F/≠t32) 5CH2- -OCO- (linking group described in West German Published Patent No. 1t2A3/j) -CO- (%Application No. 1987-72371 (linking group described in No.) R21 is a hydrogen atom, a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, anisono group, an acylamino group, a ureido group, a cyan group, a nitro group , sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, cycloalkyl group, alkanesulfonyl group, arylsulfonyl group or acyl group 1 R22 is a hydrogen atom, an alkyl group, an alkenyl group, It represents an aralkyl group, a cycloalkyl group or an aryl group.

V represents all the atomic groups forming a j-membered or t-membered ring.

ps and q each represent/and may be the same or different when λ.

When l is 2, R21 may form a fused ring sound.

zl is a covalent linking radical such as a heterocycle, unsubstituted frozen or substituted arylene, linear or branched alkylene, -CH2-, -CH2CHCH2- Ha -CH2-CH-CH2- -CH2-CH2-CH2-CH2 - -CH2CH-CH2-CH2- 2H5 -CH2CH2-0-CH2-CH2-Z2 represents a divalent heterocyclic residue.

L2 represents a linking group.

For example, -(CH2month(0〇- 〇-(CHz3 OC- 17≠- - (CH2), -OC-NH- OO NHC(CH2)a C0- -(CH2)p-COOCH2CH2SO2-NCOO
- -N-Coo- 薯-7! - However, d is an integer from O to io1, preferably 0-1? represent.

Wl is a hydrogen atom, a halogen atom, an alkyl group having 1 to 101 carbon atoms, preferably / to j, an alkanamide group having 1 to 101 carbon atoms, preferably / to j, an alkoxy group having 1 to 10 carbon atoms, preferably /-1; Group, number of carbon atoms/~10. Preferably /~j alkoxycarbonyl group, aryloxycarbonyl group, carbon number /~101 preferably /~j alkanesulfonamide group, aryl group, carbamoyl group,
It is selected from N-alkylcarbamoyl groups having carbon atoms of /-10, preferably / - O, nitro groups, cyan groups, arylsulfonamide groups, sulfamoyl groups, imido groups, and the like.

W2 is a hydrogen atom, an alkyl group, an aryl group, or an alkenyl group with a carbon number of up to t, W3 is a hydrogen atom, a halogen atom, a nitro group, an alkoxy group with a carbon number of up to t, or an alkyl group, and p is an alkyl group. Represents all integers from O to B.

X and Y are a hydrogen atom, an alkyl group or an arkenyl group, preferably having carbon atoms/~101, preferably 7~
Straight-chain, branched-chain or cyclic alkyl groups, alkenyl groups, etc., preferably have all substituents, and substituents include halogen atoms, nitro groups, carbon numbers /
-1 alkoxy group, aryloxy group having t to 10 carbon atoms, alkanesulfonyl group having 1 to 1 carbon atoms, carbon number &-
10 arylsulfonyl groups, carbon number l~! Alkanamido group, anilino group, benzamide group, alkyl-substituted cartumamoyl group, carbamoyl group, carbon number /~ O, aryl-substituted carbamoyl group, carbon number 1
- an alkylsulfonamide group having t to 10 carbon atoms, an alkylthio group having t to 10 carbon atoms, an arylthio group having t to 10 carbon atoms, a phthalimide group, a succinimide group, an imidazolyl group, /, 2. ≠−
Triazolyl group, pyrazolyl group, benztriazolyl group, furyl group, benzthiazolyl group, alkylamino group with carbon number/-4, alkanoyl group with carbon number l to t, benzoyl group, alkanoyloxy group with carbon number/~≠, Benzoyloxy group, perfluoroalkyl group with carbon number/~g, cyan group, tetrazolyl group, hydroxy group, carboxyl group, mercapto group, sulfo group, amino group, carbon number l
- an alkylsulfamoyl group having 6 to 10 carbon atoms, an aryloxy-substituted carbonyl group having t to IO carbon atoms, an imidazolidinyl group, or an alkylidene amino group having carbon number/-A.

The alkanamide group ifc represented by The substituent may be selected from the substituents listed above for the alkyl group and alkenyl group.

The alkoxy group represented by X has carbon atoms l to i in detail.
o, preferably represents a straight chain, branched chain or cyclic alkoxy group with carbon number/~, and may have a substituent group, such as the substituents listed above for the alkyl group or alkenyl group. 7g = Choose from.

The aryl group represented by Y is a phenyl group or naphthyl group, and the substituents include the substituents listed above for the alkyl group or alkenyl group or the number of carbon atoms/-1
selected from alkyl groups, etc.

The heterocyclic group represented by Y includes a diazolyl group (2-imidazolyl group, ≠-pyrazolyl group, etc.), a triazolyl group (/, 2.≠-triazol-3-yl group, etc.), a thiazolyl group (λ-benzothiazolyl group, etc.) ), oxacylyl group (/, 3-oxazole-coyl group, etc.), pyrrolyl group, pyridyl group, diazonyl group ('+μm diazin-λ-yl group, etc.), triazinyl group (/, λ, Hiro-
triazin-3-yl group, etc.), furyl group, diazolinyl group (imidazoline-choyl group, etc.), pyrrolinyl group, chenyl group, etc.

b is 0. /or λ, C represents O or l.

Is at least one of X and Y a water-soluble group or its precursor? Motsu. Examples of the water-soluble group or its precursor are shown below: -COOH or its salt, -COOH, -COOCFa, carboxylic acid ester group such as -NH8O2CHa, sulfonamide group such as -NHC
Carbamide groups such as OOCH3, -NHCOOC2H5, -802N
H2s (where R1 is a hydrogen atom or a straight chain or branched alkyl group with a carbon number of /~Hiroshi, R2 is a straight chain or branched alkyl group with a number of carbon atoms of /~H), and the total number of carbon atoms of R1 and R2 is r or less ) Next, specific examples of compounds represented by the general formula [■] will be given. However, it is not limited to this.

-I/1 The DIR coupler used in the present invention has development inhibiting properties according to the effects described above and a tendency not to substantially inhibit silver bleaching properties, and among them, the following general formulas [■] and [■] ,
Compounds represented by [X], CX['l, [■], [X■] to [X■] are preferred.

General formula [■] 〇General formula [■] -r +2- General formula [X [] General formula [x■]] General formula [X■] General formula [X■] Ru-C0-CH-co-NH-R42 General formula (ff'
] -r! - General formula [X■] (Coo-Y)b General formula [X■] rt - In the formula, X and Yl have the same meaning as already defined in the general formulas [■] and [■].

In the formula, R11 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R12 and RlB each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R11 is preferably a carbon atom, substituted or unsubstituted, linear or cyclic,
It may be either. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amine group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R11 are: isoprobyl, isobutyl, tert-butyl, isoamyl,
tert-amyl group, l, /-dimethylbutyl group, l,
l-Dimethylhexyl M, /, /-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, λ-methoxyisopropyl group, λ-phenoxyisopropyl group, 2ptert-ithylphenoxyisopropyl group, α-aminoisopropyl group group, α-(
These include diethylamino)isopropyl group, α-(succinimido)isopropyl group, α-(phthalimido)inpropyl group, α-(benzenesulfonamido)isopropyl group, and the like.

When R11, R12 or RIB has a phenyl group in c% of aromatic groups, the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups. , an alkyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. It may be substituted with a phenyl group or an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamido group, or an arylvreido group,
The aryl group portion of these substituents may be further substituted with one or more alkyl groups having a total carbon number of l-coco.

The phenyl group represented by R11, R12 or R13 may further include an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, including those substituted with a lower alkyl group having a carbon number of - It may be substituted with a halogen atom.

Further, R11, R12 or R111 may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a chromanyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents.

When R11 represents an alkoxy group, the alkyl moiety represents a linear or branched alkyl group, an alkenyl group, a cyclic alkyl group, or a cyclic alkenyl group having a carbon number of / to aO, preferably 1 to JJ; It may be substituted with a halogen atom, an aryl group, an -r-taralkoxy group, or the like.

When R11, R12 or R13 is a heterocyclic group, each of the heterocyclic groups is connected to the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the nitrogen atom of the amide group through one of the carbon atoms forming the ring. Join. Such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole,
Thiazole, oxazole, triazine, thiadian,
An example is oxazine. These may further have a substituent on the ring.

In the general formula [X], R15 represents a linear or branched alkyl group (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl group, etc.) having a carbon number of ≠01, preferably 1-2, or an alkenyl group ( For example, allyl group), cyclic alkyl group (for example, t is cyclopentyl group,
cyclohexyl group, norbornyl group, etc.), aralkyl group (e.g. evabenzyl, β-phenylethyl group, etc.), cyclic altanyl group (e.g. evacyclopentenyl, cyclohexenyl group, etc.), and these represent halogen atoms, nitro groups, cyano groups, etc. group, aryl group, alkoxy group, aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylarylsulfonyl group, alkylsulfonyl group, arylthio group , an alkylthio group, an alkylamino group, a dialkylamino group, an aniline group, an N-arylaniline group, an N-alkylaniline group, an N-acylaniline group, a hydroxy group, a mercapto group, and the like.

Furthermore, R15 may represent an aryl group (eg, phenyl group, α- or β-naphthyl group, etc.). The aryl group may have one or more substituents, and examples of the substituent include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group,
Aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkyl It may have an amine group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc.

More preferred as R5 is at least one ortho position.
A phenyl group in which each group is substituted with an alkyl group, an alkoxy group, a halogen atom, etc., and is useful because the coupler remaining in the film is less likely to fade due to light or heat.

Furthermore, R15 is a heterocyclic group (for example, a !- or t-membered heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom as a petro atom, a fused heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.), a heterocyclic group substituted with the substituents listed for the above-mentioned aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group,
It may also represent an arylcarbamoyl group, an alkylthiocarnozomoyl group or an arylthiocarbamoyl group.

In the formula, R14 is a hydrogen atom, carbon number 1 to ≠01, preferably 1-2- straight chain or branched alkyl, alkenyl,
Cyclic alkyl, aralkyl, cyclic alkenyl groups (these groups may have the substituents listed for R5 above), aryl groups and heterocyclic groups (these groups may have substituents listed for R1 above).
It may have the substituents listed for 5. ), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.), aralkyloxycarbonyl group, alkoxycarbonyl group, aryloxy group, alkylthio group, arylthio group, carboxy group, acylamino group, Diacylamino group, N-alkylacylamino group, N-diarylacylamino group, ureido group, urethane group, thiourethane group,
Arylamino group, alkylamino group, cycloamino group, heterocyclic amino group, alkylcarbonyl group, arylcarbonyl group, sulfonamide group, carbamoyl group, sulfamoyl group, cyan group, hydroxy group, methcapto group, halogen atom, and sulfo group Represents either.

In the formula, R7 represents a hydrogen atom or a linear or branched alkyl group, alkenyl group, presently an argyl group, an aralkyl group, or a cyclic alkenyl group having 1 to 3 carbon atoms, preferably Fi/ to 2 carbon atoms. and these are the above R1
It may have the substituents listed for 5.

R17 may also represent an aryl group or a heterocyclic group, which may have the substituents listed above for 'Ris.

-ta≠- In addition, R17 is a cyan group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, a ryoryloxycarbonyl group, an acyloxy group,
Sulfo group, sulfamoyl group, carbamoyl group, ryosylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, ryolthio group, alkylthio group, alkylamino group, dialkylamino group group, anilino group, N-
It may also represent an arylanilino group, an N-alkylanilino group, a hydroxy group or a mercapto group.

'Rts, R19 and 12G each represent a group used in a conventional high-equivalent phenol or α-naphthol coupler; specifically, R8 is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon residue, an acylamino group, - 0-R31 or -8-R31 (however, R31 is an aliphatic hydrocarbon residue), and when there are more than 0 P, 18 in the same molecule, two or more 118 are different groups. The aliphatic hydrocarbon residues include those having substituents.

Examples of R19 and R20 include groups selected from aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues, or one of these groups may be a hydrogen atom, and these groups may have substituents. Including those with.

Further, R19 and R20 may jointly form a nitrogen-containing heterocyclic nucleus. r is an integer of l-≠, S is an integer of 1 to 3, t
is an integer of /-1. The aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or straight chain.

and preferably an alkyl group (e.g. methyl, ethyl,
propyl, isoptetravir, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.), alkenyl groups (eg, allyl, octenyl, etc.). Typical aryl groups include phenyl and naphthyl groups, and typical heterocyclic residues include pyridinyl, quinolyl, chenyl, bilysyl, and imidazolyl. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, Examples include groups such as aryloxy, arylthio, acyloxy, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino.

R11% of substituents of couplers represented by general formula [■] to [XV:] R12s R13s R14s R15
, R17, R18, R19, and R20 may be bonded to each other, or any one of them may be a covalent group to form a symmetrical or asymmetrical composite coupler.

Examples of couplers used in the present invention include, but are not limited to, the following compounds.

More specifically, the patent application No. 1/1986/JJ Riwo,
Examples include compounds described in No.-7JJ7J' and Japanese Patent Application Laid-open No. Sho to-irry, to.

Particularly preferred DIR carbs for use in the present invention include the above-mentioned exemplified compounds (2), (3), (4), (
6) is a DIR coupler that releases a development inhibitor having a carboxylic acid ester bond. When these couplers are separated in the emulsion film during development, their low molecular weight makes them highly diffusive and brings about a favorable glabella multilayer effect. Furthermore, when it moves into the developer, it undergoes alkaline hydrolysis and becomes a harmless compound, so there is little inhibition of desilvering.
It is an IR coupler.

In the light-sensitive material of the present invention, the coating amount of the DIR compound is the coating amount of photosensitive silver halide in terms of silver/, Ofatashij? ×
When the silver iodide content of the photosensitive silver halide is 10' mol or less, preferably 1 x 10-4 mol or less, and the silver iodide content of the photosensitive silver halide is λ mol or less, preferably 1 mol or less, it is about 3 minutes or less. This is advantageous in preventing desilvering inhibition due to bleach-fixing.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkaline dispersion method, preferably a latex dispersion method, and a more preferable oil-in-water dispersion method. This can be cited as a typical example. In the oil-in-water dispersion method, tar is dissolved in either a high-boiling organic solvent with a boiling point of /7j0C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, and then dissolved in the presence of a surfactant. It is then finely dispersed in an aqueous medium such as water or an aqueous gelatin solution. Examples of high boiling organic solvents are described in U.S. Pat. No. 2,322,027 and others.

Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. tgl.

No. 27≠ and No. 2 of the same. Jul, No. 230, etc.

The compound represented by the general formula (1) or CII) not only has little or no inhibitory effect on the bleach-fixing of reduced silver, but also has a weak inhibitory effect on the progress of development in gradation areas, especially the legs, during color development. It has the advantage that the multilayer effect works effectively in the mid-tone to high-density areas.

When a DIR coupler is not used, the bleaching and fixing inhibiting effect of reduced silver is extremely small, so that the bleaching and fixing process of the color light-sensitive material of the present invention can be completed in about 2 minutes or less, even in 1 minute. Reinforcement of weaknesses caused by not using DIR couplers, such as layered effects, image sharpness, etc.
It is desirable to supplement the granularity improvement with other means. The multilayer effect is achieved by applying a masking method using colored couplers.
For example, an overlaying effect from a red-sensitive layer to a magenta-producing green-sensitive layer can be imparted by adding a magenta dye release compound to the red-sensitive layer. Image sharpness can be imparted by using a colored coupler or the like that imparts a blur mask. Grain improvement can be supplemented, for example, by the combination of competing couplers or by the combination of a portion of a coupler forming a diffusive chromophore.

There are sensitizing dyes that are preferably combined with the present invention. Sensitizing dyes that do not inhibit color development or inhibit the bleaching and fixing effects of reduced silver are preferably used. The types of sensitizing dyes used include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, hemicyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Sensitizing dyes having the effect of inhibiting color development, bleaching of reduced silver, and fixing, especially the latter, are cationic cyanine dyes, especially sensitizing dyes absorbed by J aggregates. However, when a substituent having a water-soluble group is introduced into the N-substituent or C-substituent of the cyanine dye, the inhibitory effect is significantly reduced. Anionic cyanine dyes have almost no inhibitory effect. The same properties are shown for hemicyanine dyes and logocyanine dyes; merocyanine dyes have less inhibitory effect than cationic cyanine dyes, but similarly, the inhibitory effect can be almost eliminated by introducing a substituent with a water-soluble group. Can be done.

In the present invention, a sensitizing dye having a substituent having a precursor of a water-soluble group is used in a raw color light-sensitive material, and after image exposure, the substituent having a water-soluble group is hydrolyzed in the color development process. It is possible to eliminate the bleach-fixing inhibiting effect of reduced silver. These sensitizing dyes are preferably used in combination.

In particular, in color light-sensitive materials for photography, monomethine cyanine dyes, trimethine cyanine dyes, simple merocyanine dyes, dimethine merocyanine dyes, irarapentamethine cyanine dyes, and hemicyanine dyes may also be used. A substituent is introduced into the N atom or C atom of this bone nucleus. The sensitizing dye used in the present invention has the following general formula [
Particularly preferred are those into which a substituent represented by X■] is introduced.

General formula CXV) -(Zl)-r(Lz), Y Here, Zl is preferably the above-mentioned alkylene group or alkoxyalkylene group having a carbon number of / to l.

io+2- L2 and C have the same meaning as shown in general formula (I), Y
is a hydrogen atom or a group having at least a water-soluble group or a precursor thereof, and e represents O or l.

A specific example is shown below. However, it is not limited to this.

CH2-C0OH.

-CH2-C00C2Hs, -CH2CH2-0H1 -CH2CH2-8OaH.

-CH2CH2CH25OsHs H3 -CH2CH2CH-CH2-S Os H1-CH2
-CH2-CH2-C00CHs, -COOCHs, -CH2CH2CH2S 02 CHs, etc.

Preferably, it is a group that can be hydrolyzed in a color developer and converted into a strongly water-soluble group.

Specific examples of the sensitizing dyes used in the present invention include the compounds described in Japanese Patent Application No. 61-2930j3 +g/pages JJ.

The sensitizing dye used in the present invention can be added after being dissolved in a water-soluble organic solvent. It can also be added after being solubilized in a surfactant. Further, the chemical sensitizer can be added to the silver halide emulsion in an amount of 0-5 to 1xlO-3 mol per mol of silver. In the present invention, in particular, before chemical sensitization or during grain formation, 1) liter per 7 moles of silver is added.
It is preferable to add it in an amount of y, io' to 1×10 −2 molar amount.

By this method, high sensitivity can be achieved in silver halide containing zero silver iodide over approximately 1 mole φ or less. The sensitizing dye according to the present invention can be added in a larger amount than usual, and can provide spectral sensitization as well as the effect of preventing irradiation.

The light-sensitive material of the present invention uses a transparent support. Films of appropriate thickness such as cellulose acetate films and polyethylene terephthalate λ-axis stretched films can be used.

The reflective support that can be used in the present invention is preferably one that enhances the reflectivity and clearly compresses the dye image formed in the silver halide emulsion layer.Such reflective supports include titanium oxide, titanium oxide, Examples include those coated with a hydrophobic resin containing dispersed light-reflecting substances such as zinc, calcium carbonate, and calcium sulfate, and those using vinyl chloride resin containing dispersed light-reflecting substances as a support. For example, baryta paper,
Polyethylene coated paper, polypropylene synthetic paper, transparent support with a reflective layer or a reflective material,
Examples include polyester films such as polyethylene terephthalate, cellulose triacetate, and cellulose nitrate, polyamide films, polycarbonate films, and polystyrene films, and these supports can be appropriately selected depending on the purpose of use. ! Fta Tokukai Sho to-xio
No. 3≠, special application No. A/-/lrJ'00, No. 61-
/1rroi, etc., or the specular reflection described in No. 210
j A support having a kind of diffusely reflective surface is used.

A transparent support is also used in the present invention.

Photographic additives that can be used in the light-sensitive materials of the present invention are described in the following Research Disclosures /74≠3 and /17/l at specified locations and in the patents cited therein.

IOA-l chemical sensitizer, 23N taza page right side 2
Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-2 layer, page t-r right column - super sensitizer
A4Z? 4th layer column ≠ Brightener
, 2-layer page! Kabushi prevention agent 2μ~2! Page tμ page right column and stabilizer light absorber, 2j ~, 2 layer page tl page 19 right column ~ Luther dye ultraviolet t page 0 left column line absorber 7 stain inhibitor, 2 layer page right column tro page Left to right R Dye image stabilizer, page 21 Hardener Colo page Ajt/page left column 1
0 no 2 inder 2 to 100 same as above 1/
Plasticizer, lubricant page 27 tto page right column l Coating aid, surface page 2t-27 Same as above Activator 13 Static prevention, page 27 Same as above agent The photosensitive material of the present invention has an antihalation layer on the support, an intermediate There can be layers, each halogenated photosensitive layer, one filter layer, a protective layer, an auxiliary layer, etc., and seven layers on the opposite side of the support.

Further, in order to achieve both high sensitivity and high image quality and also improve color reproducibility, the following layer arrangement can be adopted. For example, the description in Japanese Patent Application Sho t/-, 2311 J/I-1:8 and U.S. Pat.

/, 2, ++X-@, No. a, ltt, olt, British Patent No. 1. Taro 0. Tough J, US Patent No. G.

/l't, 0// No. +, 267.264 No., No. μ
, /73,117 No. 4', /,? 7.9/7 issue,
No. 44. /ljt, No. 23, British Patent No. 2. /,
31゜96+2, Tokukai Sho! 9-/77.63, No. 1,
British Patent No. J, /37,37J, Japanese Patent Application
o, s, rtr issue, same! Tar20≠, 03g issue and Tokukai Sho! Tar/60. /J! Description of issue, etc.

Cyan-forming coupler in the red-sensitive emulsion layer and magenta-forming coupler k,'l! in the green-sensitive emulsion layer. Generally, each of the sensitive emulsion layers contains a yellow-forming cazoler, but an anisotropic combination may be used depending on the case. For example, infrared-sensitive layers may be combined for use in pseudo-color photography or semiconductor laser exposure.

It is preferable that the amount of coating silver used in the photosensitive material of the present invention be as small as possible in order to shorten not only color development but also bleaching, fixing, or bleach-fixing steps. From a comprehensive viewpoint of image quality such as sensitivity and granularity, when using a transparent support, 2 m2 is converted to silver.
2 or more, 2-t or less, preferably 20? Furthermore, irt
The following are preferred.

Similarly, in the case of a reflective support, it is preferably lf or more and ioy or less, preferably lrr or less, and more preferably Fiit or less.

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. As the color developing agent, p-phenylenediamine compounds are preferably used, although phenolic compounds are also useful, and representative examples thereof include 3-methyl-guriminnow N, N-diethylanily-7O-turn, 3-Methyl-guamino-N-ethyl-N-β-human tetracylethylaniline 3-methyl-guamino-
N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methylder-amino-N-ethyl-N-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, and p-)luenesulfonates.

These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developing solution may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, and inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. It generally contains an inhibitor. In addition, if necessary, preservatives such as hydroxylamine or sulfate, organic solvents such as triethanolamine and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, and pigments are also added. forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary nucleating agents such as l-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids,
Various chelating agents such as aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, West German patent application (OLS) No. 2. Antioxidants such as those described in No. 10 may be added to the color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybencephs such as hydroquinone, /-phenyl-
3-pyrazolidones such as 3-pyrazolidone tft is N
Known black-and-white medicines such as aminophenols such as -methyl-p-aminophenol can be used alone or in combination.

In particular, for quick and easy color development, for example,
- Kotj/Geta issue, Akirat/-Core! ! As described in No. 7, etc., a restoring agent for the oxidized color developing agent (Rege
It is preferable to use a color developing solution characterized by containing both a nerator) and a capture agent for its restoring agent.

The restoring agent and the capturing agent for the oxidized product of the restoring agent are the color developing agent used, for example, 3-methyl-μm amino-N-ethyl-N
-(β-methanesulfonamidoethyl)aniline can be used. When the active ingredient used changes, the conditions can be changed and defined based on common chemical knowledge, such as by adjusting the number of moles.

For example, the restoring agent is a hydroxylamine derivative, for example, Japanese Patent Application No. Sho J/-/91917, Sho 61-/u7F22,
Showa 4/-/rtjjI issue, Showa t/-1Ir&! ! Hydrazine derivatives such as No. 3, for example, patent application ShoA / - /
7θ7! The compound may be selected from the compounds described in Japanese Patent Application No. Sho J/-/7/612, Sho T/-/7J4tAr, and the like. The capture agent is a triethanolamine derivative, for example, as disclosed in Tokuhan Sho t/-/It! tO issue, Showa t/-20
7j'l! The compound can be selected from the compounds described in No. 1997/97≠20, etc.

Next, we will explain how to specify "restorer" and "capture agent".

Regulations for reducing "restorer" of oxidized product of color developing agent Prepare the following test solutions A, B, and C, mix equal amounts of test solutions A and B, and stir gently for 10 minutes at room temperature. . After passing the mixed liquid through the mouth, the mixed liquid was designated as D and 3 of liquid D and liquid C were added.
The absorbance (C302 and D302) at 0 nm was measured.

Test solution A: Potassium phosphate 0.0/mol Sodium sulfite 0.213-Methyl-guamino-N-ethyl-N-(β-methanesulfonomidoethyl)-aniline 3. Of silver oxide 7.47f add water
ioθ0-pH is prepared with hydrochloric acid or potassium hydroxide.

Test solution D solution l potassium phosphate 0.0! Morou//J
- Add test compound 7 x 10 = molar water to tooodpH'7. O pH is adjusted with hydrochloric acid or potassium hydroxide.

Test solution C phosphoric acid/potassium 0.01 mol Sodium sulfite o, 1t3-methyl-l-
Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline /, jf Add water to omlp
H7,.

Prepare with pH-adjusted hydrochloric acid or potassium hydroxide.

A test compound with D302/C302 of o, rθ or less was defined as a restoring agent.

The "Regenerator IJ" of the color developing agent according to the present invention is an oxidized product of color developing agent 3-methyl-deramino-N-ethyl, N-(β-methanesulfonamidoethyl)-aniline in an aqueous solution. It refers to a compound that has the property of reducing and returning the substance to its original state.Also, the restoring agent itself has the characteristic that it is difficult to be oxidized and decomposed in the coexistence with the trapping agent. Test solutions E and F as specified below were prepared.

2CO32zt Exemplary compound I-(Jj) μ, 2f Test compound o, or mol pI (10
,Ko! The ESR spectrum of Test Solution F and Test Solution E, which did not contain the test compound, was measured using a measuring device.

Compare the spectral intensity of liquid E and that of liquid F, and find that the spectral intensity (SR) of liquid E is that of liquid F (SF).
A test compound with an R o4 or less compared to > was defined as a capture agent. In test solution E, the restorer is easily/electronically oxidized by oxygen in the air in a few minutes. There is no need to use an oxidizing agent.

The measurement conditions for ESR were as follows.

(1) Central magnetic field 337t G (Gauss), t
(7Q (2) Measured temperature, 2!0C (3) Microwave output g mW (4) Modulation Modulation of 0.t3G for a frequency of 10 kHz.

(5) Response 0.1 (6) Increase rate 100 times
ger ) J refers to a compound that has the property of reacting with the l-electron or λ-electron oxidized product of the restoring agent in the alkaline aqueous solution used and returning it to the original state of the restoring agent.

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

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents include compounds of polyvalent metals such as iron (■), cobalt (I [[), chromium (■), and copper (II)], peracids,
Quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; iron (I[)
or copal) (I[), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, methyliminodiacetic acid, l,3-diaminopropanetetraacetic acid, cyclohexanediaminetetraacetic acid, or citric acid, tartaric acid, Iron salts of organic acids such as malic acid; persulfates; bromates; manganates and the like can be used.

Among these, the preferred method of using bleach from the viewpoint of speeding up bleaching is to use bleach solution/,! -diaminopropanetetraacetic acid iron(I[) complex salt, iron(III) in citric acid or tartaric acid
Iron with a high redox potential (strong oxidizing power) like salt (■)
salt, or an aminopolycarboxylic acid iron (■) complex salt with a relatively low redox potential, such as an ethylenediaminetetraacetic acid iron (TII) complex salt, and a compound that can quickly oxidize the reduced form of these, such as the above-mentioned persulfate. , bromate is used in combination.

Further, it is a preferred embodiment for use of a bleach-fixing solution that performs bleaching and fixing at the same time, and for rapid processing.

A preferred bleaching agent for use in a bleach-fixing solution must not only have strong oxidizing power but also be able to coexist stably with the fixing agent to some extent. Examples of such bleaches include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Examples include iron(I) complex salts of cyclohexanediaminetetraacetic acid.

It is preferred to use bleach accelerators in the bleach solution, bleach-fix solution and their pre-baths.

Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and -III- In particular, compounds having a mercapto group or a disulfide group are preferred, as described in US Pat. RSR No. 1, West German Patent No. 1
, 290. I/, No. 2, Tokuko Sho J/-/991! No. 6/-, 2, 2j? The compounds described in this issue are preferred.

Further preferred are the compounds described in US Pat. No. a, rrs, rJa. These bleach accelerators may be added to the photosensitive material. When bleaching and fixing color photosensitive materials for photography,
These bleach accelerators are particularly effective.

Examples of the fixing agent include thiosulfates, thiocyanates, thioureas of thioether compounds, and large amounts of iodides, but thiosulfuric acid sulfate is commonly used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

Bleaching and fixing according to the present invention are preferably carried out as a bleach-fixing (Blix) solution.

The inhibitory effect on bleach-fixing was determined by using a sample in which a certain amount of silver was deposited on a film containing a silver halide emulsion In.
It is immersed in a specified bleach-fix solution for a certain period of time, washed with water, and the amount of residual silver is measured. The inhibitory effect can be demonstrated by allowing a predetermined amount of the compound to coexist with silver halide in the silver halide emulsion layer and measuring the increase in the residual amount.

A preferred desilvering step for developed silver after color development in the present invention is incorporated as a step including bleach fixation 1 (Blix). For example, steps such as development → bleach-fix → stabilization or water washing, development → bleach → bleach-fix → stabilization or water washing are used.

Therefore, the evaluation of the inhibitory effect on desilvering was tested using a bleach-fixing process. All samples are prepared in which a silver halide emulsion photosensitive layer is provided on a film support, and a test sample is prepared in which a certain amount of silica-reduced silver is produced by development.

It is immersed in a specified bleach-fix solution for a certain period of time, washed with water, and the amount of residual silver is measured and used as the measured value. On the other hand, film samples are prepared by adding predetermined amounts of various compounds to the silver halide emulsion. A film sample with a predetermined amount of developed silver is prepared in the same manner as the sample described above, treated with the same bleach-fix solution, washed with water, and the amount of residual silver is measured. The inhibitory effect on bleach-fixing can be evaluated by comparing the amount of residual silver in a standard sample and various samples. Furthermore, by determining the amount of silver remaining after color development using various color photosensitive materials and determining whether or not it is within the allowable amount, it is possible to evaluate whether or not desilvering is inhibited. The allowable amount of residual silver is approx. μ
It is preferable that it is about g/an2 and 3 μg/cm2 or less.

In the present invention, the term "amount that does not substantially inhibit silver bleaching" means that the amount of residual silver after processing is approximately 9 minutes to 1 minute, excluding the time required for the drying process. ! It refers to the amount of DIR compound used that is reduced to less than μg/am2.

Typically, in a continuous bleach-fixing process using EDTA iron rII [) complex salt as a bleaching agent and ammonium thiosulfate as a fixing agent, as typified by the bleach-fixing solution in Examples/3 below, 33- 4140 for 1 to 2 minutes in the maximum developed silver area, preferably! The silver halide color photographic light-sensitive material of the present invention is characterized in that silver bleaching or desilvering properties are not substantially inhibited when residual silver of μg/crn 2 or more is not generated. After treatment, it is common to wash with water and/or -/+2/- to perform stabilization treatment.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
al of the Society of Mo
tion Picture and Televis
ion Engineers Volume A4L, P.

It can be determined by the method described in 2ar N2z3 (Iqzr Year! Month issue). Usually, the number of stages in the multistage countercurrent system is preferably 2-6, particularly preferably 2-6.

According to the multi-stage countercurrent method, the amount of water used for washing can be greatly reduced, for example, by 0.5 ml per m2 of photosensitive material. jI, -/L or less is possible, but the increased residence time of water in the tank causes problems such as bacteria propagation and generated floating matter adhering to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
/6J, No. 2-/+2.2-, the method for reducing calcium and magnesium can be used very effectively. Also, JP-A-Sho J-
Inthiazolone compounds and thiabendazoles described in No. 7-114-, chlorine-based disinfectants such as chlorinated sodium incyanurate described in No. 6/-/20/4Z7, patent application No. 1986-10! ≠! 7) IJ Azole, and others by Hiroshi Horiguchi, ``Chemistry of antibacterial and antifungal agents'', Hygiene Technology Joint Line ``sterilization of microorganisms, sterilization, and antifungal technology'', Japan Antibacterial and Antifungal Research Line ``Bacterial Antifungal Agents'', It is also possible to use bactericidal agents described in "Encyclopedia of Bacterial and Antifungal Agents".

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound such as formalin, or a film suitable for stabilizing the dye.
Examples include buffering agents and ammonium compounds for adjusting to H. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, a surfactant, a fluorescent whitening agent, and a hardening agent may be added.

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. For this purpose, it is preferable to use various precursors of color developing agents.

For example, the indoaniline compounds described in US Pat. No. 3.3μ2,397, US Pat. No. 3.3≠co,! Tata issue, Research Disclosure l≠rlO issue and same/! /jf
Schiff base-type compounds described in No. 9, aldol compounds described in Deco≠ No. 13, metal salt complexes described in U.S. Patent No. J, 7/9.1792, and urethane compounds described in JP-A-131621. Various salt-type precursors can be mentioned.

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

Various processing liquids in the present invention are used in to'C-to'c. 33°C or 3. Although the roC temperature is standard, it is possible to increase the temperature to a higher temperature to accelerate processing and shorten the processing time, or conversely to a lower temperature to improve image quality and stability of the processing solution. Furthermore, in order to save silver on photosensitive materials, treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2,1.2J, 770 or U.S. Patent No. 3.J7&4 (29) is carried out. It's okay.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount or 3o4 or less for cost reduction and the like.

Next, specific processing steps of the present invention are shown below, but the steps of the present invention are not limited to these.

8 Color development - bleaching - (washing with water) constant fixing - (washing with water) - (stable) 0 color development - bleach-fixing - (washing with water) - (stable) 3, color development - bleaching - bleach-fixing - (washing with water) - (stable) ) t1 Color development - Bleach - Bleach fixing - Fixed - (Water wash) - (Stable)! 0 color development - bleaching - constant - bleach fixing - (washing) - (stable) Although it can be omitted depending on the application, it is not preferable to omit water washing and stabilization at the same time in the final process.

Particularly preferred is development processing using a processing solution stream.

In the silver halide photosensitive material of the present invention, the silver iodide content of the photosensitive emulsion layer is 2 molar or less, preferably 1 molar or less,
Furthermore, by selecting an appropriate DIR coupler and reducing its usage, it is possible to maintain excellent color reproducibility and sharpness while still producing high-speed negatives that can be developed quickly and quickly desilvered. Processing liquid for the photosensitive material in the mold)
By combining and using the IJ-M Genrin processing system, the characteristic performance of the present invention can be exhibited.

In particular, it is important to reduce the amount of ions released from photosensitive silver halide during color development and the amount of development inhibitors generated from DIR couplers.
[) Since it eliminates the bleaching inhibition caused by salt and the fixing inhibition caused by sodium thiosulfate, rapid development processing is possible especially with high-sensitivity photographic negative light-sensitive materials with a large amount of coated silver.

When the developing processing method of the present invention is used not only in large laboratories but also in mini-labs, negative processing can be completed without waiting, resulting in great economical effects.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A color development processing system using a processing liquid stream according to the present invention, particularly a color development machine, will be specifically described.

FIG. 1 schematically shows the functions of the color development processing section according to the present invention. A color photosensitive material, such as a film (S), is fed into a development processing path by conveyance rollers (R, R1, R2, R3, R4, R5). A color developer stored in another sealed stock tank is injected into the development processing path through an injection hole P1 in accordance with the film feeding speed, and flows out through an overflow hole (01) for the color developer. Therefore, the film is transported through a stream of color developer at a speed that is preferably slower than the transport speed of the film, and processing is always started with fresh processing solution, resulting in exhausted color developer being discharged near the overflow hole. . Preferably, the transport rollers R1, R3, R5, and R6 serve as drive rollers. It is then fed into the bleach-fix path. A new bleach-fix solution is injected through the bleach-fix injection hole (P2), and the exhausted solution flows out through the overflow hole (02). Next, the film is fed into a stabilizing bath or a rinsing bath, and immediately after passing the transport roller R5, it enters a rinsing bath processing path. New rinsing liquid is injected into the rinsing bath processing path through an injection hole (P3) and flows out into a discharge hole opened in the rinsing bath, and the rinsing bath is filled with oats and flows out through one hole (03). The film is rinsed with fresh rinsing liquid, drained by a blade plate (B) and sent to the drying chamber (V).

The drying chamber is fed through the inlet hole (P4) and the exhaust hole (04).
More exhaust. In this way, the color processed film (T) is wound up. While the color developing solution, bleach-fixing solution, and rinsing solution are stored in a stock container for consumption, they are stored compactly using a container that is separated by a free thin film so that the drained solution can also be stocked. . The drive unit is completely smooth and smooth for developing machines.
It's hard to believe.

The color development processing system according to the present invention can be combined with the above-mentioned color negative development processing section, color photographic paper development processing section, and printing section. To this end, techniques used in conventional minilab systems are used.

The length and arrangement of each processing path can be adjusted according to the color development process, or it can be applied in combination with conventional liquid temperature processing.

FIG. 2 shows a typical developing machine for processing color negative film.

-l+22- In Fig. 2, C: constant temperature bath W; washing tank D: color developing tank S; stabilizing tank Bl: bleaching tank
R; Roller B2; #I
i: Inlet of the photosensitive material F: Fixing tank Io: Represents the exit of the photosensitive material.

The film enters from If, passes between the rollers of the developer tank,
After passing through the narrow nozzle and the lower roller, it again passes through the parallel narrow path, passes between the rollers, and exits the developer tank. Similarly, it passes through a bleaching tank, a fixing tank, a washing tank, a stabilizing tank, and finally enters a drying zone.

An example of the present invention is shown. However, it is not limited to this specific example.

Example-/ Sample 10/ was prepared on a cellulose triacetate support, consisting of each layer of surface acid as shown below.

1st layer: Emulsion layer Pure silver bromide emulsion (grain size 0.7μ, octahedral grains) Silver coating amount: 00 f/m2
Coupler A θX/(7-2 mol per mol of silver) Second layer: Protective layer polymethyl methacrylate particles (diameter approximately 1.

In addition to the above composition, a gelatin hardening agent H-/ and a surfactant were added to each layer of gelatin skin containing ztim).

The compound coupler used to prepare the sample was an emulsified dispersion of coupler containing 1ooy and color image stabilizer Cpd.
-j's toy, Cpd-p's 31't with 0il-/
And Oi! -2 mixture/30ml and ethyl acetate 100ml
ml of a mixed solution, and this solution was dissolved in a 70% aqueous gelatin solution containing sodium dodecylbenzenesulfonate≠Of.
It can be emulsified and dispersed in 200f.

α Cpd-J Cpd-≠ H-/: (CH2=CH8O2CH2CONHCH2÷Next, DIR coupler was added to sample 10/, or iodine was added to the pure silver bromide emulsion with the same grain size and size distribution. By using an emulsion uniformly containing 1 molti, λ molti, and ≠molti, samples 102 to 1≠O with the compositions shown in Table 1 were obtained.
was created.

-/JJ- DIR Coupler B DIR Coupler C DIR Coupler D DIR Coupler E The samples prepared in this manner were subjected to centrimetry exposure and then processed as follows.

Table-2 Processing process A Processing time Processing temperature Replenisher color development 2
min q o 'C/, zL/m2m white fixing
J minute ao 'C1, ot/m2 whole process! The composition of the treatment solution used is as follows.

Pentaacetic acid i, o i,.

l-Hydroxyethylidene/, /-diphosphonic acid 3.0 3.0/, J-diaminopropanol ≠, Og, O Sodium glutamate j, O! ,
0-/3bu-λ- Potassium carbonate 30.0 30.6Potassium bromide/G-hydroxylamine sulfate Co,7 3.0Hiro-(N-ethyl-β-hydroxyethylamino)-comethylaniline Sulfate ≠, j j, 0 Add water /, Ol /, 0 l-pH Add sodium hydroxide 10. Oj 10. ≠! (Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate salt jO,0 Ethylenediaminetetraacetic acid disodium salt r.

Sodium sulfite /, 2.0-/J
7- Ammonium thiosulfate aqueous solution (70%)
%)! , Ogo bleach accelerator
Add 0.01 mol water
/, 0L pH 6,0 In the developing machine according to the present invention shown in FIG.
Bleach-fix solution f/70r is injected from injection hole P2 at a flow rate of
The water was injected at a flow rate of rtl/min, and in this embodiment, ion-exchanged water was injected from the injection hole P3 at a flow rate of rtl/min. The film transport speed is /,! It was rILZ minute.

The flow rate of the treatment liquid stream at this time was as follows.

Table 3 In Figure 1, the bathtubs for color development, bleach-fixing, and ion-exchange water treatment baths have the same size at the entrance and exit. ×0
．． /jα width. Moreover, the tank length of each bathtub is 2゜1 g, 2, A r for color development, bleach fixing, and washing.
rL, /, 3 m te$fc. The tank liquid volume at this time is /, j! t,/,jTjt, 0°11.

The opening degree at this time is /, × 10 ``cm''; /, × lOc for color development, bleach-fixing, and washing with water.
rrL;3. It was t×10 crfL.

As a comparative example, development was carried out in the same manner as in B) A) using a processing solution in a conventional tank type developing machine.

Height 1 for color developer, bleach-fix solution, and water washing.

λm x length 4tOcrrL x width 3 (:'crILi /
, J'mX4'OCR×30crrL; / ,
2@x20pXJ 0 (yl container and combined liquid lθo
t; 10otHrot.

The opening degree of this tank-type development is /,,2 for each mixed solution.
×1O−2crn”;/, 2×10 “fi”;
/,,2×1O-2(zl).

A) B) Each automatic processor was filled with the solution and its initial photographic performance was examined, and the combined solution was left for ≠ weeks and developed again.

The photographic properties obtained and the results of liquid analysis of the color developing solution are shown in the following table.

Sampling the color developer after processing! After standing for a while, the solution was removed from the center of the tank.

-/≠O- -/4t/- In the developing method of the present invention, the initial photographic properties of the present invention are o, ox-o, compared to conventional processing methods.

7th place is high feeling. Moreover, even after two rounds of running, the method of the present invention maintains high sensitivity, whereas the conventional method had a sensitivity of 0. /! It has become lower. Therefore, when the replenishment amount was 20% of the conventional amount, it was found that the sensitivity remained constant in the λ round. Therefore, the treatment method of the present invention is more sensitive and stable than conventional methods, and can be treated without preparing a replenisher.

Furthermore, when comparing the photographic properties after aging for ≠ weeks, the conventional method has an average of 0.2/~/r low sensitivity, but the present invention has an average of 0.2/~/r.
It can be seen that 03 has a low sensitivity and is a stable process.

The analysis results also show that the method of the present invention shows little deterioration when turning deep red after several weeks of aging, and is a simple and hassle-free treatment system.

Example 2 Sample 30/, which is a multilayer color negative light-sensitive material Q, was prepared on an undercoated cellulose triacetate film support with each layer having the composition shown below. The silver halide emulsions (1) to αε used were prepared as follows.

First, a silver halide emulsion (A) was prepared as follows.

(Liquid 1) (Liquid 2) Sulfuric acid (/N) A Hongd (Liquid 3) Compound A of Experiment (1) (Liquid) 3 (Liquid) 174t Gu (Liquid) (Liquid) (7 Heat liquid) (/liquid) to 52°C, add (liquid 3) and (liquid 3), and then. Thereafter, (liquid 4) and (liquid J) were added simultaneously over a period of lμ minutes. After a further 70 minutes, (liquid 6) and (liquid 7) were added at the same time for flj minutes. Addition! After a few minutes, the temperature was lowered and desalination was carried out.

Add water and dispersed gelatin, adjust the pH to t, 2, average particle size 0.4 tfμm, coefficient of variation (standard deviation divided by average particle size Hs/d) - lg! - A monodispersed cubic silver chloride emulsion with θ of 10 was obtained. Sodium thiosulfate was added to this emulsion at rr 0c to perform optimal chemical sensitization, and the above-mentioned CR compound was added to silver halide/mol ≠ × 1 OmOI to perform spectral sensitization. In addition, B as a stabilizer is silver halide/mo1/9!
×10 mol was added.

Emulsion (A) is prepared by adding the following (liquid) for 70 minutes after adding (liquid 2) and (liquid 7), and then cooling down after 5 minutes. Emulsion (B) ).

(R solution) Emulsion (A) is made by adding the following (Resolution) and (IO solution) to the liquid (A) and (7) for 11 minutes, respectively, and then adding the following for 11 minutes. After io minutes, the following (ll solution)
An emulsion (C) was prepared in which emulsion (C) was different in that the emulsion and (I solution) were added over 5 minutes and the temperature was lowered 1 minute later.

(Liquid) (IO solution) (II solution) (7,2 solution) Next, add the following (/3 solution) and ( /≠liquid) were used to prepare emulsion (D).

(3 liquids) (14 L liquids) Next, emulsion (A) is made by adding the previously mentioned silver bromide ultrafine grain emulsion (grain size O1O!μ) to silver chloride before chemical sensitization. /mo1% of silver bromide was added, rr
Emulsion (E) differing only in that it was aged at 0C for 70 minutes
was prepared.

Furthermore, emulsion (E) is a compound in which CR compound (2), silver tetragenide/mol (t) II, OX/0'mo is added before adding the silver bromide ultrafine grain emulsion. An emulsion (F) differing only in the following was prepared.

Stabilizer B -II Goo Compound A H3 In the method for preparing emulsion A, the grain size is changed by changing the temperature during grain formation, and emulsions (1) to (6) are optimally chemically sensitized with sodium thiosulfate. ) was obtained.

[Preparation of Emulsions (7) to az] Grain formation was carried out in the same manner as Emulsions +11 to (6), and sodium thiosulfate, chloroauric acid, and rhodan ammonium were added during chemical ripening to obtain Emulsions (7) to Q21.

[Emulsion (131-αa)] Grain formation was performed in the same manner as in Emulsions (1) to (6) to form Emulsion (F).
After adding the CR compound according to the preparation method of
After adding λmol of Br (0,0jμ) per mole of silver halide and mixing and ripening at sr 0c for 10 minutes, sodium thiosulfate was added to give the emulsion (+3 )-(tQ was obtained.

[Emulsion alpha snout]

For emulsion 09-0 seconds, in addition to sodium thiosulfate,
Chloroauric acid and rhodanammonium were added and chemical ripening was performed to obtain an emulsion (In-(24)).

(Composition of photosensitive layer) The coating amount is the amount expressed in silver r/m2 for silver halide and colloidal silver, and 1! for couplers, additives and gelatin. The amounts are expressed in m2 units and, for sensitizing dyes, the number of moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal steel...0.2 Gelatin.../, J colored coupler C-/...0.01 Ultraviolet absorber UV-/・・・・・・0.1 Same as above UV-2・・・・・・Ol, 2 Dispersion oil 0
il-/ ・・・・・・θ, θ/Same as above
0i1-J ・・・・・・0.0/th layer (
Intermediate layer) Fine grain silver chloride (average grain size 0.07μ) ・・・・・・0. /j gelatin ・・・・・・／, 0 colored coupler C-λ ・・・・・・O, O, 2 dispersion oil 0il-/ ・・・・・・0.7 3rd
Layer (first red-sensitive emulsion layer) Emulsion (1) The number is listed in the table (
Average particle size O0φμ.

Fluctuation rate 0. /co)...Silver/, 0 sensitizing dye I
....../, J x 10' Sensitizing dye ■ ...... J, j x 10 ' Sensitizing dye ■ ....../,! ×10-5 Coupler C-3...Ol, 2≠Coupler C-μ
...0.2g coupler C-r
...0.0g coupler C-2 old...θ, Og dispersion oil 0il-/ ...0. /
! Same as above 041-J ・・・・・・0.
0.2nd ≠ layer (second red-sensitive emulsion layer) Emulsion (2) No. is listed in the table (
Average particle size 0.7μ.

Fluctuation rate 0.10) ・・・・・・Silver 7.0 Gelatin ・・・・・・i,.

Sensitizing dye I.../×10
'Sensitizing dye II (CRR compound) ・・・3×/θ
-4 Sensitizing dye I [1 (CRR compound) ....../X
10” Coupler C-1, -1-0, Or Coupler C-7...0./Dispersion oil 0il-/...0.0
/ Same as above Oil ・・・・・・o、
Orth! Layer (middle layer) Gelatin.../, 0 Compound Cp d -A...0.
0.3 Dispersion oil 0il-/・・・・・・
o, or th layer (7th green-sensitive emulsion layer) Emulsion (3) Listed in Table 4 (
Average particle size o, aμ.

Fluctuation rate 0,'/,2)...
Silver O4♂sensitizing dye■ ・・・・・・r×
10' Sensitizing dye■ ......λ
×10'-/! Knee coupler C-ta...dan 0.23 coupler C-/...0.03 coupler C-1o...0.0/!
Coupler C-r...0.0
! Dispersion oil 0il-/ ・・・・・・0.
2 Seventh layer (second green-sensitive emulsion layer) Emulsion (4) (Average grain size 0.7μ.

Fluctuation rate 0.70) ・・・・・・Silver o, r tagelatin ・・・・・・／
, 0 sensitizing dye■ (CR compound...3.!×10
'Sensitizing dye ■ ・・・・・・/, '1X10
'Coupler C-// ・・kawa・0.
0/Coupler C-/J ・・・・・・0
．． 03 Coupler C-/, y... Group 0
．． 20 coupler C-t...
0.0.2 coupler C-7!・・・・・・
・0.02 dispersion oil 0il-/・・・・
...0.20 Same as above Oil ...
... o, or g layer (yellow filter single layer) 17 ta 3- gelatin ... /, 2 yellow colloidal silver ... θ, or compound Cpd-B ...・0. /Dispersed oil 0il-/...0.3rd layer (first blue-sensitive emulsion layer) Emulsion (5) The number is listed in the table (
Average particle size O0≠μ.

Variation rate O, /2) ・・・・・・Silver O0≠gelatin ・・・・・・／, 0 sensitizing dye■ ・・・・・・Co×10' Coupler C-7 Hiromu ・・・・・・・O, Ta coupler C-, t...0.07
Dispersion oil 04l-/・・・・・・0.2
1st O layer (2nd blue-sensitive emulsion layer) Emulsion (6) No. is listed in the table (
Average particle size 0.7μ.

Volatility rate o, 10) ...Silver O2! Gelatin ・・・・・・o, sensitizing dye■ ・・・・・・／X/117
'Coupler C-t≠ ・・・・・・0.2
Dispersion oil 0il-/ ・・・・・・0.
07 1st/layer (1st protective layer) Gelatin...O0? Ultraviolet absorber UV-/・・・・・・0. /Same as above UV-λ ・Old...0.2 dispersion oil 0il-/...0.0 layer Dispersion oil Oil -, 2...0.07 1st 2nd layer (
2nd protective layer) Fine grain silver chloride (average particle size 0.07μ)...O,j Gelatin...0.4t
! Polymethyl methacrylate particles (diameter/, jμ)... Group 0.2 hardening agent H
-/... Group O, lI Formaldehyde Scavenger S-/... o, r Formaldehyde Scavenger S-2... θ, j In addition to the above components, each layer contains a surfactant. was added as a coating aid. The C-z c-is -t ■ CH2 ■ C(CH3)3 C-ta (e mol, wt, approximately 20,000 C-/) prepared as described above.

1/r-ti C-/2 α ito- C-/J α C-/≠ pdA pdn Sensitizing dye ■ Sensitizing dye ■ (CR-compound) Sensitizing dye ■ (CR-compound) Same as cpd-2 above -Compound) Sensitizing dye ■ (CR-Compound) 1/13- Sensitizing dye ■ H-/ CH2=CH-802-CH2-CONH-CH2CH
2=CH-802-CH2-CONHCH2H -7A≠- In samples 30/ to 3011, typical examples from emulsion preparation companies to F are (A, ) and (F).
Then, chemical sensitization was selected to prepare emulsions (1) to 2a)f, and each emulsion was combined as shown in Table 6 to obtain sample 30/I-JO4t.

Using tungsten light as a light source, exposure to μIr000 using a color temperature changing filter at 2 jCMS ///
After exposure for 0.00 seconds, color development was performed in the following steps.

I got the following results. The photosensitivity was based on sample 30/ as shown in Table 7, and sample 30μ had a photosensitivity that allowed photography.

Table 7 These photographic elements used a tungsten light source and the color temperature was adjusted to fllr000KK with a filter.
After giving an exposure of ioθ seconds, 3
Development processing was performed at r0C.

Table-! Color development 10 minutes/io seconds bleaching 3 minutes/j seconds bleaching
3 minutes! Fixation in seconds J minutes O seconds Washing 3 minutes It seconds Stabilization 7 minutes 01 seconds The composition of the processing solution used in each step was as follows.

Pentaacetic acid 1. or(haoBl-hydroxyethylidene-1,/-diphosphonic acid 2.09(2,09) sodium sulfite, 0ff(!, OS')-/A
7- Potassium carbonate, A 3o, op (3r, oy
) Potassium bromide 841 (0,99) hydroxylamine sulfate ko, 4t? (3,,tt) Hiro-
(N-ethyl~N-β-hydroxyethylamine)-comethylaniline sulfate g, rf (r, cof) Add water and 801 (801) H/ 0.0 (1
) H10,3 bleach solution (replenisher) Ethylenediaminetetraacetic acid ferric ammonium salt 100.0? (100,0f) Ethylenediaminetetraacetic acid disodium salt 10. Of (10, Of) ammonium bromide lro, of (/rty, of) ammonium nitrate lo, of (lo, ofl add water /, Op (/, o7) -/lr
- pH4.0 (pH!, J) Fixer (replenisher) Ethylenediaminetetraacetic acid disodium salt /, 09 (/, 09) Sodium sulfite u, Of (11,0?) Ammonium thiosulfate aqueous solution (7o4) /7J- , oml(lyz,
owl) Sodium bisulfite 11.1. ? (g, 6t) Add water 1. ol(/, 01
) pH &, 6 (pH 1, A) Stabilizer (Replenisher) Formal y (1704),! , oml(,2,om
ll polyoxyethylene-p-mo//nylphenyl ether (average degree of polymerization to lo, 3t (o, 3t
) Samples 30/~3o Hiro treated with water were measured for concentration using red light, green light, and blue light. The results obtained are shown in Table 7. In Table 7, the relative sensitivity is the relative value of the exposure amount required to provide a density corresponding to [minimum density factor 〇, λ] expressed as an antilog.

According to Table 7, Sample 303 of the present invention is similar to Comparative Examples 301 and 30.
Sample 30μ, which was chemically sensitized with high chloroauric acid, was even more sensitive, and the effect of the present invention is clear.

The automatic developing machine used in Example 2 was a rack-type automatic developing machine shown in FIG. The film feed speed is p
tσ/min, and processing solution replenishment is color development /, jl/
m2; bleaching (cascade processing)/, 117m2;
Fixing/, /l/m2; Washing o, ll/min; Stable/, /l
/m2.

The liquid capacity of each tank is 0.47 for color development! ; bleaching 0.9
1. Fixing/2Il; washing with water 0.91; stability 0.31. The area in contact with the processing liquid and air for each tank is tcr
Therefore, the opening degree of each tank is I×1.
0 “crn”;17×10-3crn-1;! ×
10crn;Otsu, 7×l0-2crII-1;ko×lO
It was cIn.

As in Example 1, the stability of the solution was good, and it was found that rapid processing and stable processing could be obtained by combining it with the present sensitive material.

Note that the time for each step is as follows.

Color development 2 minutes/10 seconds bleaching 3 minutes/j seconds x 2 fixing
μ minutes, 20 seconds of water washing, 3 minutes of lj seconds, stability, 1 minute of OJ' seconds. For faster processing, replace the rack shown in Figure 1 with a rack with a shorter path.

Example-3 A silver halide emulsion (G)' was prepared as follows.

Solution (liri bone gelatin 309NaC
/! 3. If H201OOOCc NH4NO33r Solution (#) AgNO3/! riNH4NO3o,t? Add H20 /jOc12 solution (/7) Nacl t, 3? H2
Add C1 /! OCc solution (nr) AgNO313rtNH4NO3i
Add H20'e and azoCc solution (/li) NaCl zi, 7? H2
Add 0 to t, trocc solution (lr) and keep at 27 r 'C, add IN sulfuric acid to adjust the pH to 0, then add solution (/, t)-
2. While stirring vigorously, add solution (/l) and solution (/7)f.
They were added simultaneously over a 20 minute period. Next, solution (lr) and solution (19) were added simultaneously over μθ minutes, but at an accelerated rate such that the final flow rate was three times the initial flow rate.

0,/N sulfuric acid was added in a controlled manner to keep the p)T of the reactor constant. In the case of preparation of emulsion (G) -/7.2
- When adding solution (lr) and solution (19), a solution (x)'fr of compound (1) having the following structural formula dissolved in 100 x 2xoocc of methanol was simultaneously added at a constant rate. Furthermore, addition of solution (yr) and solution Cl9) is completed 1
CR/Compound 31O of structural formula (co) from the minute before the end to the end
A solution (,2O) prepared by dissolving (1) in a mixed solution of H2O and methanol (310 mL) was added at a constant rate.

CR compound (,2) The emulsion () prepared in this way has an average grain size of 0.1
They are 2 μm octahedral particles. This emulsion has a large light absorption peak at ≠t4 Anm and a small light absorption peak at 77 nm. Emulsion (H)' was prepared in the same process as emulsion (G). However, the amount of compound (1) added is 2! I made it ■.

Emulsion A has an average size of 3 .mu.m and is a heptahedral grain as shown in photo X2.

Emulsion (G) and temperature! Particles were made using almost the same process except that the temperature was lowered to 0.00, then washed with water using the usual 70 curing method, desalted, gelatin was added, and the pH was adjusted to 6.0 at ao 0C. p to λ
Ag was adjusted to 7.0. The emulsion is a nest-dispersed emulsion with octahedral grains, an average size (equivalent sphere diameter) of 0.70 μm, and a grain size variation coefficient of 10.

The emulsion (λ6) made according to the method of emulsion fH) is (//
/ One face is a lg-hedron with a jj ratio, and the average size is 0°7λμ
m1 coefficient of variation is 9. Emulsion (C) was cubic with an average size of 0.73 μm and a coefficient of variation of 9. Each emulsion was chemically sensitized using diphenylthiourea and gold chloride. The amount of chemical sensitizer is shown in Table 1. Emulsion (stiffness is thiosulfate) IJium sulfur sensitizer per 7 moles of silver halide)
ixto-6 moles, gold chloride 30X10 per 7 moles of silver
'Mole used.

The emulsion (cot) was similarly chemically sensitized using a sulfur sensitizer and a gold sensitizer.

In the sample (30μ) in Example-1, the emulsion (,
Emulsion (, zA ) was used instead of emulsion (2μ), and emulsion (2
In place of 2), emulsion (21), sensitizing dye Vl (CR compound) and V? Using. Also, emulsion (2J') and sensitizing dyes ■, II (CR compound) and m (CR compound) were used instead of emulsion (, 2 (7)), and emulsions (19) and (21
) and (3) by adjusting the chemical ripening conditions for the sample (
3O evening) I wrote it all.

Imagewise exposure was carried out in the same manner as in Example 2, and color development processing according to the present invention was carried out by rapid processing using a processing solution stream. A sensitivity approximately 10 times higher than that of the sample (3OU) was obtained.

Next, preferred embodiments of the invention will be described.

(1) At least one layer of the silver halide photosensitive layer group consists of silver bromide, silver chloride, or silver chlorobromide, the average silver iodide content of which is below the gmol coefficient or which does not contain iodized steel. A color development processing method according to the claims, characterized in that an emulsion is used and a sensitizing dye or DIR compound having a substituent group represented by the following general formula (I'1) is contained.

General formula (I) + L 2+1f-Y In the formula, L2 is a linking group and C is O?/1 When C is O, L
2 represents a bond. Y represents all water-soluble groups or precursor residues thereof.

(2) At least one IHC in the silver halide photosensitive layer group
A color development method according to claim 1, characterized in that a vertex-developable silver halide (CDG) emulsion defined by .

Here, a CDG emulsion is one in which the silver halide grains in the emulsion are cubic or /≠hedral grains with jloo> faces, or r-hedral grains with (///) faces, and are used for color development processing. In the characteristic curve of the emulsion obtained by the developer and the development temperature, the silver image was exposed for 7750 seconds at an exposure amount corresponding to =/'#- (maximum density - maximum/J% density) After the development has started, a diluted aqueous solution of glacial acetic acid is poured in and stopped, and at that time, at least 70% of the silver halide grains that have started development are at the apex of the ridge and its vicinity, and when 14 is a hedral grain, (///) refers to an emulsion that is controlled to be developed on the surface.

(3) A color developing method according to the claims, characterized in that an edge-developable silver halide (EDG) emulsion defined in at least one layer of the silver halide photosensitive layer group is used.

Here, EDG emulsion means that the silver halide grains in the emulsion have substantially the same aspect ratio! The above tabular grains were exposed for 1,710 seconds at the exposure amount specified in the CDG emulsion specifications, and after the development started, it was stopped using a J-4 aqueous solution of glacial acetic acid, and at that time development started. It refers to an emulsion in which at least 704 of the silver halide grains are controlled to be developed at and near the edges and vertices of the average grain.

At +411sO sensitivity! Or tao.

After imagewise exposure, the color photosensitive material is heated for 1 to 9 minutes.
A color development processing method according to claim 1, characterized in that the color development processing is carried out for a period of minutes.

[Brief explanation of drawings]

FIG. 1 shows a sectional view of a color developing machine according to the present invention. The film S is conveyed through the transport rows 5-R%R1, R2, R3, R4,
Conveyed by R5, R6 and R. Development processing zone Dev, bleach-fixing zone B11x. After passing through a stabilizing bath zone and a drying zone, color development processing is carried out. Each processing liquid is injected through the injection ports P1, B2, and B3 and flows out through the overflow holes 01, 02, and 03. There is an exhaust hole 04 where the film that has passed through the stabilizing bath St is drained of water by a blade plate B and dried by air sent from an air hole P4. Note that M is a machine room. FIG. 2 shows a sectional view of a color developing machine according to the present invention. In FIG. 2, C; constant temperature bath D; color developing layer B1; bleaching bath B2; IF; fixing layer W; washing layer S; stabilizing bath R; represent. FIG. 3 shows the relationship between the solubility capacity of the processing liquid tank and the tank opening degree in the acid color developing machine, and the color developing machine position X (as described in Example 2) and Y (as described in Example 2) according to the present invention.
7)'f: Show. Patent Applicant Fuji Photo Film Co., Ltd. Figure 1 OEV Day 1iX Procedural Amendment

Claims (1)

[Claims] (1) A color photosensitive layer comprising, on a support, a silver halide photosensitive layer containing a yellow coupler, a silver halide photosensitive layer containing a magenta coupler, and a silver halide photosensitive layer containing a cyan coupler. Using materials,
In a color development processing method including imagewise exposure, color development and/or simultaneous desilvering treatment, at least one layer of the silver halide photosensitive layer group contains silver halide or silver bromide having an average silver iodide content of 4 mol% or less. , using an emulsion consisting of silver chlorobromide or silver chloride, and at least one step of the color development process being exposed to substantially free air to a processing liquid stream having a flow rate different from the transport speed of the color light-sensitive material. 1. A color development processing method characterized in that the color development processing method is carried out by contacting the surface of the silver halide photosensitive layer side of the color photosensitive material without being exposed to the silver halide photosensitive layer.