JPH022553A - Method of processing silver halide color negative film and processing agent kit set for the same film - Google Patents

Abstract

PURPOSE:To obtain the same sensitometry curve even at an arbitrary temp. by incorporating a p-phenylene diamine color developing agent having a water soluble group at a specific ratio or above into a color developing soln. and executing processing by changing the color developing time according to the processing temp. of the color developing soln. CONSTITUTION:The p-phenylene diamine color developiong agent having the water soluble group is incorporated into the color developing soln. at least at >=2.0X10<-2>mol per 1l color developing soln. and the processing is executed by changing the color developing time according to the processing temp. of the color developing soln. in the method of processing the silver halide color negative film with the color developing soln. after exposing. The same sensitometry curve is obtd. in this way by adjusting the color developing time even at the arbitrary temp.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for processing a silver halide color negative film (hereinafter also simply referred to as color negative) and a color negative processing agent kit set, and particularly relates to a processing method during processing. The present invention relates to a color negative processing method and a color negative processing agent kit set capable of obtaining rapid and stable photographic performance regardless of temperature fluctuations.

[Background of the Invention] In order to obtain a color negative image by processing a color negative that has been imagewise exposed, a color development step is followed by a bleaching, fixing or bleach-fixing process to desilver the metallic silver produced, and then Processing steps such as water washing, stabilization or water washing substitute stabilization, and image stabilization are provided.

Generally, color negatives are sent by users to mini-labs, large-scale labs, etc. for development, where they are processed in automatic developing machines under predetermined conditions at a constant temperature and for a certain amount of time. However, in fields such as the press, where it is necessary to convey new news to readers as quickly as possible, reducing time by one minute or one second holds the key to meeting the manuscript deadline. . For this reason, in order to save time in the press, it is preferable to develop the film on-site rather than processing it in a laboratory.
It is often sent by wire to the head office, and in that case, the hobby kit 1
They go to the site with - and carry out the treatment in the bathrooms of hotels and inns. However, they are unable to control the temperature and generally maintain the standard temperature of 38℃, so the treatment takes a long time at a low temperature. This is the current situation.

Therefore, there were problems in that the quality became unstable due to long-term development, and that the quality of prints from color negatives was unsatisfactory, and that the development process took too long and the immediacy of the news was lacking.

Also, color negatives have a maximum sensitivity of 11iAsA or 100,20
The number of types has increased to 0°400.3200, and it has been desired to develop a processing agent that can finish uniformly at any desired temperature.

[Object of the Invention] The first object of the present invention is to provide a processing method in which the same sensitometric curve can be obtained by adjusting the color development time even at any temperature; An object of the present invention is to provide a processing agent kit set having explanatory notes indicating the relationship between a color developer suitably used in carrying out the processing method, processing temperature, and processing time.

[Structure of the Invention] The processing method of the present invention that achieves the above object is a method of processing a silver halide color negative film with a color developer after exposure, using a p-furinyl diamine color developer having a water-soluble group. The main ingredient is at least z, ox per 1 stand of color developing solution.
to-" moles or more, and is processed by changing the color development time depending on the processing temperature of the color developer, and the processing time is within 6 minutes when the processing temperature of one color developer is 30 ° C. do.

In addition, the processing agent kit set of the present invention that achieves the above-mentioned object includes a p-phenylenediamine-based color developer main agent having a water-soluble group at least z, ox t per color developer.
It is possible to set two or more points for a color developer containing o-2 moles or more and a processing temperature for a color developer using the color developer, and the color development processing temperature or the processing time at 30°C. 6
It is characterized by having an explanatory text explaining that it can be processed within minutes.

[Specific configuration of the invention] The present invention provides a color development time of yJ at two or more temperatures.
A uniform color negative finish can be obtained by processing the color negative, and the processing temperature is preferably in the range of 20°C to 40°C. A particularly preferred temperature-time relationship is the four-line section shown in FIG.

A particularly advantageous embodiment of the present invention is that silver iodide 2.
It means that it contains core-shell silver halide grains containing 0 mol % or more and/or tabular silver halide grains containing 3.0 mol % or more of silver iodide, and also contains a DIR compound.

In other words, the color development time is FA! according to two or more temperatures, that is, the processing temperature. When I tried to process what I was doing,
Color negative films using the above emulsion technology have inconsistent finishes and sensitometric gamma values of B, G,
Although the movement is different, by using the present invention, the finish is constant, and the present invention works very effectively.

The present invention will be explained in detail below.

The water-soluble group of the p-phenylenecyamine-based compound having a water-soluble group of the present invention includes at least one water-soluble group on the amino group or benzene nucleus of the p-phenylenecyamine-based compound. is (C11□),, -(:II, Oll, -(C11
□)lI-NIISO□-(CIL), 1-(:I(+
+, -(CI+□), -0-(CI+2). -CHf
f, -((:H2(:H2O), IC,112=,,(
l and n each represent an integer greater than or equal to 0. ), -CO
Preferred examples include OH group, -3o, and II group.

Specific examples of color developing agents preferably used in the present invention are shown below.

[Example color developing agents] N.L. +! H.

Hz N.H.

11H1 N.H.

N.H.

1Hz N.H.

MHz )+1(.

Among the color developing agents exemplified above, preferred for use in the present invention are exemplification Nos., (B-1), (B-2), and (B-
3) , (B-4), (B-6), (B-7) and (B
-15), particularly preferably No.
, (B-1).

The color developing agent mentioned above is usually a hydrochloride or a sulfate.

It is used in the form of salts such as p-toluenesulfonate.

The p-phenylenecyamine compound having a water-soluble group used in the present invention has a concentration of 2, Dx 10 per liter of color developing solution.
-” mol or more, preferably 2.Ox
The range is from 10-'' to 2.5X 10-' moles, more preferably: 1.Ox 10-'' to 1. Ox is in the range of 101 moles.

The color developer of the present invention may contain the following developer components in addition to the above components.

As an alkaline agent, for example, sodium hydroxide potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc. may be used alone or in combination to achieve the E effect, that is, precipitation. They can be used together as long as they do not occur and maintain the pl+ stabilizing effect. In addition, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium carbonate, and borates are used for purposes such as pharmaceutical needs or to increase ionic strength. I can do something.

Furthermore, inorganic and organic antifogging agents may be added as necessary.

Furthermore, a development accelerator can also be used if necessary. As a development accelerator, U.S. Patent No. 2.548,6
No. 04, No. 3,671,247, Special Publication No. 1971-1995
Various pyridinium compounds typified by Publication No. 03,
Other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat.
2,950,970, z, so, tz 7, and nonionic compounds such as polyethylene glycol, derivatives thereof, and polythioethers described in Japanese Patent Publication No. 44-9504; Contains organic solvents and organic amines such as ethanolamine, ethylenediamine, jetanolamine, and triethanolamine.

Also, phenethyl alcohol described in US Pat. No. 2,304,925, as well as acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, and ammonia.

Examples include hydrazine and amines.

In the present invention, it is preferable to use an organic or inorganic inhibitor in the color developing solution.

The organic inhibitor in the present invention is a nitrogen-containing polycyclic compound,
Compounds containing a mercapto group, aromatic compounds, onium compounds, and compounds having an iodine atom as a substituent, preferably the following general formula (R-1), CR-11)
and f: R-111).

The compound represented by the general formula CR-1) is more preferably a compound represented by the general formula CR-I'/) or (R-V), and most preferably the compound represented by the general formula [R-Vl
) to (R-XI).

On the other hand, for the compound represented by the general formula (R-11), the most preferred is the general formula [R-■] or [RXT[[
] It is a compound represented by.

General formula (R-1) In the formula, x and X+ are a halogen atom, an alkyl group, an aryl group, an amino group, a hydroxyl group, a nitro group, a carboxyl group, or a sulfonyl group, and x is a hydrogen atom, an alkyl group, an aryl group, or a ring. shows a double condensation to form . Z is a group consisting of a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom necessary to form a ring, and 1%m represents Oll or 2.

General formula (R-n) General formula [R-IV) Compounds and derivatives thereof in which 2 to 5 of 1 to 9 carbon atoms are substituted with nitrogen atoms In the formula, Y, Y,, Y,, Y are Indicates a hydrogen atom, a halogen atom, an alkyl group, an amino group, a hydroxyl group, a nitro group, a carboxyl group, and a sulfonyl group.

General formula (R-Ill) Y.

Y, -T-X.

X.

In the formula, T is a nitrogen atom or a phosphorus atom, Xl, X are a hydrogen atom, an alkyl group, an aryl group, a halogen atom, Y4, Y
represents an alkyl group or an aryl group, and Y4 and Y may be closed to form a heterocycle.

General formula [R-V] Compounds in which 2 to 4 of 1 to 5 carbon atoms are substituted with nitrogen atoms and derivatives thereof General formula [R ■] General formula [R ■] General formula [R-■] General formula [R ■] General formula [R

H ll Z 1. 2 Z15 ■ 1J31M 1B ool /\ CI, CH2C0OH (n=35-45) H +1 4G 113cI1. cH, -ClIC0OHNH7 01] C00C41L(t) OOH cH lli cH lil G59 6 l G2 l Q H H Furthermore, an auxiliary developer may be used together with the developing agent in the color developing solution of the present invention. These auxiliary developers include 1, for example, N-methyl-p-aminophenol hexulfate (methol), phenidone, N,N'-
Diethyl-p-aminophenol hydrochloride, N, N, N'
, N'-tetramethyl-p-phenylenediamine hydrochloride, etc. are known, and the amount added is usually 0.01g.
~1. Og/i is preferred.

Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multilayer effect accelerator can be used.

In addition, various chelating agents may be added to the color developer and color developer processing agent kit of the present invention, such as diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, nitrilotacetic acid, ethylenediaminetetramethylenephosphonic acid, tripolyphosphoric acid, hexamethaline. Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc. may be added.

Each component of the above color developing solution can be adjusted by sequentially adding and stirring to a certain amount of water. Generally, a plurality of components that can coexist stably are prepared in advance in a small container as a concentrated aqueous solution or in a solid state, and the mixture is added to water and stirred to obtain the color developing solution of the present invention. It's coming.

In the present invention, the above color developing solution can be used in any pH range, or from the viewpoint of rapid processing, pH 9.0 to 13.0.
pH is preferably 9.5 to 1, more preferably pH 9.5 to 1.
Used in 2.0.

In the present invention - starting with the bath treatment.

Various other processing methods may also be used, such as a spray method in which the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid. Alternatively, it is preferable that the processing step consists essentially of steps such as color development, bleach-fixing (or bleaching and fixing), washing with water (including stabilization treatment in place of washing with water), and the like.

The color developer used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal thiocyanates, alkali metal halides, pencil alcohol, and water softeners. Additionally, a thickening agent, a development accelerator, and the like may optionally be included.

Additives other than those mentioned above that may be added to the color developing solution include anti-staining agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, and the like.

In addition to the above, there are no particular limitations on the processing method for the photographic material of the present invention, and any processing method can be applied. For example, typical methods include a method in which bleach-fixing is performed after color development and, if necessary, further washing with water or stabilization treatment as an alternative to water washing; Or a method of performing water washing alternative stabilization treatment;
Alternatively, pre-hardening, neutralization, color development, stop-fixing, water washing (or water-washing alternative stable treatment), bleaching, fixing, water-washing (or water-washing alternative stable treatment), post-hardening, water washing (or water-washing alternative stable treatment)
Color development, water washing (or water washing alternative stabilization treatment), supplementary color development, stopping, bleaching, fixing, water washing (or water washing alternative stabilization treatment), stabilization in this order, development resulting from color development Any method may be used for processing, such as a development method in which the silver is subjected to halogenation bleaching and then color development is performed again to increase the amount of dye produced.

In the present invention, processing with a processing solution having bleaching ability means
means processing with a bleach solution or a bath bleach-fix solution.

Bleaching agents used in bleach solutions or bleach-fix solutions in the bleaching process are generally known to include aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid coordinated with metal ions such as iron, cobalt, and copper. There is. Representative examples of the aminobocarboxylic acids mentioned above include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenecyaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol ethercyaminetetraacetic acidethylenediaminetetrapropionic acidethylenecyaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acid pentasodium saltnitrilotriacetic acid sodium saltBleaching solution of the present invention and The bleach-fix solution is generally plI O,
It can be used at a value of 2 to 9.5, preferably 4.0 or more, more preferably 5.0 or more. The temperature of the treatment is 20
Used at temperatures between ℃ and 80℃.

The bleaching solution of the present invention can contain various additives together with the above-mentioned bleaching agent (preferably an organic acid ferric complex salt). As additives, it is particularly desirable to include alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, and the like. Also borate, oxalate, acetate, carbonate,
p)I buffers such as phosphates, solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, alkylamines, polyethylene oxides, etc. It can be added to the bleaching solution or by appropriately adding known substances.

The bleach-fix solution of the present invention includes a bleach-fix solution containing a small amount of a halogen compound such as potassium bromide, or conversely a bleach-fix solution containing a large amount of a halogen compound such as potassium bromide or ammonium bromide. It is also possible to use a fixing solution, as well as a special bleach-fixing solution having a composition consisting of a combination of the bleaching agent of the present invention and a large amount of a halogen compound such as potassium bromide.

In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. may also be used.

The silver halide fixing agents to be included in the bleach-fixing solution of the present invention include compounds 1 which react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixing agents can be used in an amount that can dissolve at least 5 g/n, preferably at least 50 g/n, more preferably at least 70 g/n.

Note that the bleach-fix solution of the present invention contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium mW acid, acetic acid, sodium acetate, hydroxide. It is possible to contain a pH 1 stabilizer consisting of various salts such as ammonium alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained. Also, hydroxyamine,
Preservatives such as hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, dicarboxylic acids, and amino acids. In step 4, an organic chelating agent such as dicarboxylic acid or a stabilizer such as nitro alcohol or nitrate, a solubilizing agent such as alkanolamine, a stain inhibitor such as organic amine,
Other additives and organic solvents such as methanol, dimethylformamide, and dimethyl sulfoxide may be included as appropriate.

Regarding the processing method using the processing solution of the present invention, the most preferable processing method is to perform bleaching or bleach-fixing immediately after color development, or bleaching or bleaching after performing treatments other than color development such as washing or rinsing and stopping. It may be fixed,
A prebath containing a bleach accelerator may also be used as a processing solution prior to bleaching or bleach-fixing.

Regarding the processing temperatures of various processing steps other than color development of the silver halide color photographic light-sensitive material of the present invention, such as bleach-fixing (or bleaching, fixing), and further washing with water or stabilization as an alternative to water washing, if necessary, 20°C to 80°C is preferred.

In the present invention, JP-A-58-14834, JP-A-58-14834;
No. 105145, No. 58-134634 and No. 58-
No. 18631 and Japanese Patent Application No. 2709 and No. 59
It is also possible to perform a stabilization treatment as an alternative to washing with water, as shown in Japanese Patent Application No.-89288.

The processing agent kit set according to the present invention includes a color development processing agent and/or a processing agent with bleaching ability, a processing agent with fixing ability (or a processing agent with bleach-fixing ability), and water washing and stabilization or washing as necessary. The set includes an alternative stabilizing solution, and the color developing agent includes a color developing agent and explanatory text, and the processing agent contains the color developing agent at a concentration of 2. O
X 10-" mole or more, and optionally contains additives such as the development inhibitor. The processing agent is
It may be separated into two or more parts liquids, or it may be in any form such as powder or paste,
Of course, even if there is a concentration that can be used as is, eli! is diluted and used. (Liquid) may also be used.

However, in the present invention, it is preferable that all of the processing agent be in the form of powder or granules, from the viewpoint of ease of handling and durability.

On the other hand, in the latter explanatory text 1, as shown in FIG.
``This process can be performed at any temperature for the color developer.Please determine the time according to the processing temperature based on the graph below.'' There is also an indication 3, such as J, indicating that the processing temperature can be set at any temperature. Yes, and a graph or table 4 showing the relationship between the temperature of the color developer and time is displayed.
The explanatory text does not need to be displayed on one sheet of paper; it may be displayed on two or more sheets of paper, or it may be displayed on a magnetic tape, disk, optical disk, or other recording medium. good.

Note that the explanatory text 1 may be attached to the processing agent container in the form of a tag or affixed in the form of a label.

In the present invention, it is preferable to provide a bleach-fixing (or bleaching, fixing) step immediately after the color development treatment step in view of speed and achieving the effects of the present invention.

Next, a color negative photographic emulsion etc. preferably used in the present invention will be explained.

First, regarding core-shell emulsions, for example, JP-A-57-
As described in detail in No. 154232, preferred core-shell silver halide grains have a core silver halide composition containing 0.1 to 40 mol % of silver iodide, more preferably 5 to 40 mol %.
The shell is comprised of silver bromide, silver chloride, silver iodobromide or silver chlorobromide, or a mixture thereof.

Particularly preferably, the shell is a silver halide emulsion containing 95 mol % or more of silver bromide as a main component.

Further, in the present invention, the preferable effects of the present invention can be achieved by making the core a monodisperse silver halide grain and setting the shell thickness to 0.01 to 2.0 gm.

The silver halide color photographic light-sensitive material preferably used in the processing of the present invention contains silver iodide in a total amount of 3.0 mol% or more, preferably 3 to 40 mol%, more preferably 4 to 15 mol%. , more preferably 5 to 10 mol%
Consisting of silver halide grains containing silver bromide, silver chloride, and especially using silver halide grains containing silver iodide as the core! A: Increasing the sensitivity of silver halide grains containing silver iodide by hiding the core of silver halide grains made of silver bromide, silver iodobromide, or a mixture thereof using a shell having the specified thickness. The aim is to take advantage of the particle's potential for and hide the disadvantageous properties of the particle. More specifically, the core is made of silver halide containing silver iodide, and the thickness range necessary to effectively exhibit only the desirable properties of this core and to shield undesirable behavior is strictly regulated. The purpose is to provide a shell to the core. The method of covering the core with a shell that has the necessary minimum absolute thickness to effectively utilize its properties can be used to change the purpose, and therefore to change the materials of the core and shell, for example, to improve or increase the shelf life. It is extremely advantageous in that it can be used for purposes such as dye-sensitive adsorption on car surfaces.

Preferably, the silver iodide content in the silver halide grains (cores) used as the matrix ranges from 0.1 to 20 mol% solid solution to mixed crystal, more preferably 0.5 to IO.
It is mole%. Further, the distribution of silver iodide contained within the core may be either unevenly distributed or uniformly distributed, and preferably low silver iodide is unevenly distributed in the center.

The silver halide emulsion having core-shell silver halide grains of the present invention can be produced by coating a shell with a core made of silver halide grains contained in a monodisperse emulsion.

When the shell is silver iodobromide, the ratio of silver iodide to silver bromide is preferably 10 mol % or less.

In order to make the core a monodisperse silver halide grain, grains of a desired size can be obtained by a double jet method while keeping pAg constant. Further, highly monodisperse silver halide emulsions can be produced by applying the method described in JP-A-54-48521. A preferred embodiment of the method is a method in which an aqueous potassium-gelatin solution and an aqueous ammonium silver nitrate solution are added to an aqueous gelatin solution containing silver halide seed particles while changing the addition rate as a function of time. It is to manufacture. At this time, the time function of addition rate, pH, pAg
A highly monodisperse silver halide emulsion can be obtained by appropriately selecting the temperature, temperature, etc.

Since the particle size distribution of a monodisperse emulsion is almost a normal distribution, the standard deviation can be easily determined. If we define the width of the distribution (%) using the relational expression, the width of the distribution that can meaningfully control the absolute thickness of the coating should preferably have a monodispersity of 20% or less, and more preferably 10%.
% or less.

Next, the thickness of the shell that covers the core is such that it does not hide the desirable qualities of the core, and on the contrary, it is thick enough to hide the unfavorable qualities of the core. That is, the thickness is preferably within a narrow range defined by these upper and lower limits.Such a shell can be formed by depositing a soluble halogen compound solution and a soluble silver solution onto a monodisperse core by a double jet method. .

On the other hand, if the thickness of the shell is too thin, parts of the core material containing silver iodide will be exposed, and the effect of covering the surface with the shell, that is, the performance such as chemical sensitization effect, rapid development, and fixing properties, will be lost. be exposed. Its thickness limit is 0. Preferably the old gll.

Further confirmed by a highly monodisperse core with a distribution width of 10% or less, the preferred shell thickness is 0. O1~0.4p+
The most preferred thickness is 0.01 to 0.2 m.

It is the highly monodisperse core that produces enough developing silver filaments to improve the optical density, that the core's ability to increase sensitivity is utilized to produce a sensitizing effect, and that rapid development and fixing properties occur. Due to the synergistic effect between the thickness of the shell regulated as above and the silver halide composition of the core and shell, if the thickness regulation of the shell can be satisfied, the shell can be constructed. As the silver halide, silver iodobromide, silver bromide, silver chloride, silver chlorobromide, or a mixture thereof can be used. Among them, silver bromide, silver iodobromide, or a mixture thereof is preferred from the viewpoint of compatibility with the core, performance stability, and storage stability.

The light-sensitive material of the present invention contains the following light-sensitive material, that is, an inner core consisting essentially of silver bromide and/or silver iodobromide in at least one light-sensitive silver halide emulsion layer; Contains negative-working silver halide grains having a plurality of outer shells provided outside an inner core and consisting essentially of silver bromide and/or silver iodobromide, and the outermost shell of the silver halide grains. High iodine content 1, in which the iodine content is 10 mol% or less, and the iodine content is 6 mol% or more higher than that of the outermost shell.
M (hereinafter referred to as a high iodine shell) is provided inside the outermost shell, and an intermediate shell having an iodine content between these two waves is provided between the outermost shell and the high iodine shell. is provided, and the iodine content of the intermediate shell is 3 mol% higher than that of the outermost shell.
The iodine content of the high iodine shell is higher than that of the intermediate shell.
It is a photosensitive material with a high mol% or more.

The above "consisting essentially of" means that it may contain silver halides other than silver iodobromide, such as silver chloride; specifically, in the case of silver chloride, the ratio is 1 mol. % or less.

The features of this photosensitive material are the following (1) to (4).

(1) An emulsion containing core/shell type silver halide grains having a high iodine shell inside is used.

(2) An intermediate shell having an intermediate iodine content is provided between the high iodine shell and the low iodine hole (outermost F?I layer) on the surface.

(3) The iodine content of the high iodine shell is 6 to 40 mol%, which is 6 mol% or more higher than that of the outermost shell layer.

(4) The difference in iodine content between the intermediate shell and the outermost shell or high iodine shell is 3 mol% or more.

Note that the three-layer core-shell emulsion described in JP-A-60-35726 can also be used in the present invention. Also, JP-A-59
-177535, 460-86659, 460-1
The core-shell emulsion described in No. 38538 can also be used in the present invention.

The photosensitive silver halide emulsion used in the present invention may be doped with various metal salts or metal complex salts during the formation of silver halide precipitates of the core and shell, during grain growth, or after the completion of growth. For example, metal salts such as gold, platinum, palladium, iridium, rhodium, bismuth, cadmium, copper or 'M salts and combinations thereof can be applied.

Further, excess halogen compounds generated during the preparation of the emulsion of the present invention, or by-products or unnecessary salts and compounds such as nitrates and ammonium may be removed. The removal method is the Tardel water washing method, which is commonly used in general emulsions.
A dialysis method, a coagulation ratio S method, or the like may be used as appropriate.

Furthermore, the emulsion of the present invention can be subjected to various chemical sensitization methods that are applied to general emulsions. Namely, activated gelatin; noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, and water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; Chemical sensitization can be carried out using a chemical sensitizer such as a reduction sensitizer such as tin or the like, either alone or in combination. Furthermore, this silver halide can be optically sensitized to a desired wavelength range. There are no particular limitations on the optical sensitization method for the emulsion of the present invention, and for example, optical sensitizers such as cyan dyes such as zeromethine dyes, monomethine dyes, trimethine dyes, or merocyan dyes are used alone or in combination (for example, supersensitization). It can be optically sensitized. These technologies are described in US patents 2 and 6.
No. 88,545, No. 2,912,129, No. 88,545, No. 2,912,129, Ibid.
No. 197,060, same: ], No. 615,635, same 1,
628,964, British Patent No. 1,195,302, British Patent No. 1,242,588, British Patent No. 1,29:1,862, West German Patent (OL S) 2,0:10. :126
No. 2.121,780, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 44-14030, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

The silver halide emulsion used in the present invention is:

In forming the silver halide grains further included,
By using a silver halide emulsion in which the core grains are monodisperse silver halide grains and coating the core grains with a shell, a monodisperse silver halide emulsion with a substantially uniform shell thickness can be obtained. Is it true that such a monodisperse silver halide emulsion can be used as is with its grain size distribution, or that two or more monodisperse emulsions with different average grain sizes can be used at any time after grain formation? It may also be used by blending the two to obtain a predetermined gradation.

The silver halide emulsion used in the present invention has a distribution width that is equal to or higher than that of an emulsion obtained by coating a monodisperse core of 20% or less with a shell. It is preferable that the silver halide grains of the present invention be included in the silver grains. However, silver halide grains other than those according to the invention may also be included as long as they do not impede the effects of the invention. The silver halide other than the one according to the present invention may be of a core-shell type other than the one according to the present invention, or may be of a type other than core-shell, and may be monodisperse or polydisperse. In the silver halide emulsion used in the present invention, at least 65% by weight of the silver halide grains contained in the emulsion are preferably core-shell silver halide grains of the present invention, and almost all of the silver halide grains are preferably core-shell silver halide grains of the present invention. It is desirable that the material be silver particles.

The purpose of the present invention is most effective when the silver halide emulsion of at least one photosensitive layer contains the following tabular silver halide grains. That is,
The emulsion of the present invention used in the silver halide emulsion layer of the present invention is either the silver halide grains or (1) core-shell silver halide grains of the present invention as described above, and (2) tabular silver halide grains of the present invention. The (tabular) λ silver halide grains of the present invention may be of core-shell type or of other types. ), (2) A mixture of the above (2) and (2) is included in the present invention.

The tabular silver halide grains of the present invention will be explained below.

The tabular silver halide grains of the present invention preferably have a grain size or grain thickness of 5 times or more. The tabular silver halide grains are disclosed in JP-A Nos. 58-113930 and 58-113934.
No. 58-127921 and No. 58-108532
In the present invention, from the viewpoint of effects on color staining, image quality, etc., the particle diameter or particle thickness is 5 times or more, preferably 5 to 1
00 times, particularly preferably 7 to 30 times. Furthermore, the particle size is preferably 0.3 gm or more, and 0.
．． Those having a pH of 5 to 6 are particularly preferably used. When these tabular silver halide grains are contained in at least 50% by weight of at least one layer of silver halide emulsion, the desired effects of the present invention are more preferably exhibited, and almost all of them are the above-mentioned tabular silver halide grains. In some cases, particularly favorable effects can be achieved.

It is particularly useful when the tabular silver halide grains or core-shell grains of the present invention are used. In the case of core-shell particles, it is preferable that they also satisfy the requirements described for the core-shell particles.

In general, tabular silver halide grains are tabular with two parallel surfaces, and therefore, "thickness" in the present invention is expressed as the distance between the two parallel surfaces constituting the tabular silver halide grain. .

The halogen composition of the tabular silver halide grains is preferably silver bromide and silver iodobromide, particularly preferably silver iodobromide having a silver iodide content of 3 to 10 mol %.

Next, a method for producing tabular silver halide grains of the present invention will be described.

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

For example, pBr 1. : In an atmosphere with a relatively high pAg value of 1 or less, seed crystals containing tabular silver halide grains of 40% or more by weight are formed, and silver and halogen solutions are simultaneously added while maintaining the pBr ratio at the same level. Obtained by growing seed crystals.

During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selection of the type and amount of solvent, the silver salt used during grain growth, the addition rate of halide, etc.

When producing the tabular silver halide grains of the present invention, by using a silver halide solvent as necessary, grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution,
The growth rate of particles can be controlled. The amount of silver halide solvent used is preferably 1 x 10-' to 1.0% by weight, particularly 1 x 10-'' to I x 10-' weight % of the reaction solution.

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

Examples of silver halide solvents that can be used include ammonia, thioethers, and thioureas. Regarding thioethers, see US Pat. Nos. 3,271,157 and 3,790. :1B7, 3,574,628, etc. may be referred to.

When producing the tabular silver halide grains of the present invention, a silver salt solution (for example, AgN0.
A method of increasing the addition rate, amount, and concentration of a halide solution (for example, KBr aqueous solution) and aqueous solution is preferably used.

These methods are described, for example, in British Patent No. 1.335,9.
No. 25, U.S. Patent No. 1,572,900, U.S. Patent No. 3.650
, No. 757, No. 4,242,445, JP-A-5514
Reference may be made to the descriptions in No. 2329, No. 55-158124, and the like.

The tabular silver halide grains of the present invention can be chemically sensitized if necessary. Regarding the chemical sensitization method, the description of the sensitization method explained for the core shell can be referred to.In particular, from the viewpoint of silver saving, the tabular silver halide grains of the present invention may be gold sensitized, sulfur sensitized, or sensitized with gold or sulfur. Combination use is preferred.

In the layer containing the tabular silver halide grains of the present invention,
It is preferred that the tabular silver halide grains are present in an amount of 40% or more, particularly 60% or more, based on the total weight of the silver halide grains in the core layer.

The thickness of the layer containing tabular silver halide grains is 0.5μ
m ~ 5.0 l 1. In particular, it is preferable that the thickness be 1.0 μm to 3.0 μm.

Also, the coating amount of tabular silver halide grains (for one side)
is 0.5g/rn' to 6g/rn', especially Ig/rn
'~4 g/m' is preferred.

Other constituents of the layer containing the tabular silver halide grains of the present invention, such as binders, hardeners, antifoggants, silver halide stabilizers, surfactants, spectral sensitizing dyes, dyes, and ultraviolet absorbers. There are no particular restrictions on 1. For example,
Re5search Disclosure+76! j3
．． Reference may be made to the description on pages 22-28 (December 1978).

Next, the structure of the silver halide emulsion layer (hereinafter referred to as upper silver halide emulsion layer) which is present outside (on the surface side) of the layer containing tabular silver halide grains of the present invention will be described.

The silver halide grains used in the upper silver halide emulsion layer are preferably high-sensitivity silver halide grains used in ordinary direct X-ray films.

The shape of the silver halide grains is preferably monospherical, polyhedral, or a mixture of two or more thereof. In particular, it is preferable that spherical particles and/or polyhedral particles having a diameter/thickness ratio of 5 or less account for 60% or more (weight ratio) of the total.

The average particle size is preferably 0.5 μw to 3 μl, and if necessary, ammonia, thioether,
It can be grown using a solvent such as thiourea.

The silver halide grains must be highly sensitive by a gold sensitization method, a sensitization method using other metals, a reduction sensitization method, a sulfur sensitization method, or a sensitization method using a combination of two or more of these. is preferred.

As with the layer containing tabular silver halide grains, there are no particular restrictions on the other compositions of the upper emulsion layer, and the above-mentioned Re
The description in 5earch Disclosure 176 @ can be referred to.

The silver halide color photographic light-sensitive materials to which the treatment of the present invention is applied are not limited to those mentioned above, but even those containing tabular silver halide grains as shown below will still have the same effect as the object of the present invention. .

For example, JP-A-58-113930 discloses a multilayer color photographic material having a dye-forming unit with a two-layer structure and having an emulsion layer containing tabular silver halide grains with an aspect ratio of 8.1 or more in the upper layer. JP-A-58-113934 discloses a multilayer color photographic material using silver iodobromide or silver bromide emulsions of tabular silver halide grains with an aspect ratio of 8.1 or more in the green-sensitive layer and the red-sensitive layer. , also published in Japanese Unexamined Patent Publication No. 58-11
No. 3927 further discloses a multilayer color photographic light-sensitive material having tabular silver halide grains having a silver iodide content or a lower aspect ratio of 8:1 or more than the central region or the annular region. JP-A No. 59-55426 discloses a silver halide photographic light-sensitive material that can be applied to color photos and contains tabular silver halide grains with an aspect ratio of 3:1 or more and a specific sensitizing dye.
Furthermore, in Japanese Patent Application No. 60-111696, the aspect ratio is 3.
A silver halide color photographic light-sensitive material containing tabular silver halide grains having at least one (III) plane and mainly consisting of (III) planes is disclosed. How can it be applied advantageously?

It is also preferable that the emulsion of the present invention contains epitaxially bonded silver halide grains as described in JP-A-53-103725 and the like.

A DIR compound is a particularly preferably used additive in the color negative of the present invention. The DIR compound is a compound capable of reacting with a fermented form of a color developing agent to release a development inhibitor.

A typical example of such an IR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting effect when separated from the active site is introduced into the active site of the coupler. For example, British Patent No. 9: No. 15,454, US Pat. No. 3,227,554, US Pat. No. 4,095.984, and US Pat. No. 4,149,886.

The above-mentioned DIR coupler has the property that, when subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler core forms a dye while releasing a development inhibitor. Also, in the present invention, U.S. Pat.
No. 41, No. 3,958,993, No. 3,961,95
No. 9, No. 4,052, 21:1, JP-A-53-110
No. 529, No. 54-13333, No. 55-16123
When a coupling reaction occurs with the oxidized form of a color developing agent as described in No. 7, etc., a development inhibitor is released.
Also included are compounds that do not form pigments.

Furthermore, JP-A-54-145135 and JP-A-56-1
14946 and 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Or so-called timing D, which is a compound that releases a development inhibitor through an elimination reaction.
IR compounds are also included in the invention.

Also, JP-A No. 58-160954, No. 58-16294
Timing DI in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent described in No. 9.
It also includes R compounds.

According to the present invention, more preferred DIR compounds can be represented by the following general formula (I) and/or (II), and among these, the most preferred DIR compound is represented by the following general formula (II).
This is a compound represented by

General formula (1) % Formula % In the formula, A is a coupler component (compound) capable of coupling with an oxidized product of a p-phenylenediamine derivative color developing agent having a water-soluble group.1 For example, acylacetanilides, acyl Open-chain ketomethylene compounds such as acetic acid esters, dye-forming couplers such as pyrazolones, pyrazolotriazoles, birazolinobenzimitazoles, indasilones, phenols, naphthols, and acetophenones, indanones, oxacylones, etc. It is a coupling component that does not substantially form dyes.

In addition, Z in the above formula is a component (compound) that is released by reaction with a -p-phenylenediamine derivative color developing agent having a water-soluble group and inhibits development of silver halide, and preferred compounds include Heterocyclic compounds and heterocyclic mercapto compounds such as benztriazole, 3-octylthio-1,2,4-)-lyazole, etc. (Heterocyclic mercapto groups include i-phenyltetrazolylthio groups, etc.) There is.

Examples of the above-mentioned heterocyclic group include a tetrazolyl group, a thiadiazolyl group, an oxadiazolyl group, a thiazolyl group, an oxacylyl group, an imidazolyl group, and a doriazolyl group. Specifically, l-phenyltetrazolyl group, 1-ethyltetrazolyl group, ]-(]4-hydroxyphenyltetrazolyl group, l,3.4-thiazolyl group, 5-methyl-1,3 , 4-oxadiazolyl group, benzthiazolyl group, benzoxacylyl group, benzimidazolyl group, 4H-1,2,4-triazolyl group, and the like.

In addition, in the above general formula (I), Z is bonded to the active site of A.

General formula (II) A2-TIME-z.

In the formula, z2 is the same as c defined in the above general formula (I). A2 also includes a coupler component which forms a completely diffusible dye as defined in general formula (I). TIME reacts with the oxidized product of A2 or the color developing agent to form the general formula (I) together with L.
It represents a timing group that can be released from the compound represented by I) and then release Z2, and T1 is represented by the following general formula (m)
, (rV).

It is represented by (V), (V'l) and (■), but is not limited to these.

General formula (m) General formula (rV) In the formula, X represents an atomic group necessary to complete the benzene ring or naphthalene ring, and Y represents 10-S-, -N-(
Here, R3 represents a hydrogen atom, an alkyl group or an aryl group, and is bonded to the coupling position. In addition, R8 and R2 each represent a group having the same meaning as the above R, or the group is substituted at the ortho or para position with respect to Y, and is bonded to the heteroatom contained in the inhibitor z2. .

In the formula, W is a group having the same meaning as Y in the general formula (m), and R4 and R are each R□ in the general formula (m).
and a group having the same meaning as R2.

R6 is a hydrogen atom, an alkyl group, an aryl group, an acyl group,
A sulfo group, an alkoxycarbonyl group, a heterocyclic residue, and R7 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amino group, an acylamido group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group,
Represents a carbamoyl group or a cyan group. This timing group is then bound by W to the coupling position of A2.

Next, an example of a timing group that releases the inhibitor Z2 by an intramolecular nucleophilic substitution reaction is shown by general formula (V).

General formula (V) Nu -E- In the formula, Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, and is bonded to the coupling position of A2. E is an electrophilic group having an electron-poor carbonyl, thiocarbonyl, phosphinyl, or thiophosphinyl group and is bonded to the heteroatom of the inhibitor Z2.

V has a steric relationship between Nu and E, and after Nu is released from A2, it undergoes an intramolecular nucleophilic substitution reaction accompanied by the formation of a 3- to 7-membered ring, and thereby the inhibitor Z2 It is a bonding group that can release .

General Formula (VT) In the formula, R8 represents a hydrogen atom, an alkyl group, or an aryl group, the oxygen atom is bonded to the coupling position of the coupler A2, and the carbon atom is bonded to the nitrogen atom of the inhibitor Z2.

General formula [■] In the formula, Y' is a group having the same meaning as Y in the above general formula (m), and R9 represents an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. Y' is bonded to the coupling position of coupler A2, and the carbon atom is bonded to the heteroatom of suppressor z2.

less than, Representative DIR compounds according to the present invention (D-3) A specific example will be described.

The invention is not limited to this. It's not something you can do.

[Exemplary compounds]

(D-1) (D-4) H (D-2) t (D-5) H ■ H3 -N (D-6) t (D-7) (D-10) t H (D-11) H (D-12) (D-13) H (D-14) 5NIJ2 (D-18) (D-15) (D-16) (D, -17) H (D-29) at (D- 30) (D-31) H (D-26) t (D-27) (D-28) C1□H2500CCHC00C1□H2s (D-34
) 0H (D-35) (D-36) (D-40) (D-41) H (D-37) t (D-38) C1□H25QC! 0CHCOOC,□)I25(D-
39) (D-42) (D (D-44) 0H (D-49) (D-50) (D-51) (D-46) (D-48) (D-56) (D-60) (D-61 t L (D-57) (D-58) (D-62) (D-63) t (D-64) 0H (D-65) H 2H5 (D-sa) CD-69) H (D-66) H (D-67) H (D-70) 02H.

02H.

(D-72) (D-73) (D-76) (D-77) (D-78) H H H (D-74) CD-75) (D-79) H C2H.

(D-82) (D-83) (D-86) CD-87) Oh.

(D-84) OH (D-85) OH -N The DIR compound of the present invention can be added to a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic constituent layer. It is preferable to add it to the silveride emulsion layer.

Two or more types of DIR compounds of the present invention may be contained in the same layer, or the same DIR compound may be contained in two or more different layers.

These DIR compounds are generally preferably used in amounts of 2.times.10-' to 5.times.10-', more preferably l.times.10-' to I.times.10-' moles per mole of silver in the emulsion layer.

In order to incorporate these DIR compounds into the silver halide emulsion or other photographic constituent layer coating solution according to the present invention,
If the DIR compound is alkali-soluble, it may be added as an alkaline solution; if it is oil-soluble, it may be added, for example, in U.S. Pat. No. 2,322,027;
No. 801,170, No. 2, 8θl, No. 171, No. 2
, 272. I'l1 and I'l1. :104,940
It is preferable to dissolve the DIR compound in a high boiling point solvent and, if necessary, in combination with a low boiling point solvent, according to the method described in each specification, disperse it in the form of fine particles, and add it to the silver halide emulsion. If necessary, two or more types of DIR compounds may be mixed and used, and the preferred method of adding DIR compounds in the present invention will be described in detail as follows.
One or more of the DIR compounds can be added to organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, triresyl phosphate, triresyl phosphate, etc. Phenyl phosphate, di-isooctyl azelate, di-loftyl sebacate, tri-hexyl phosphate,
N,N-di-ethyl-caprylamidobutyl, N,N
-diethyl laurylamide, low pentadecyl phenyl ether, sea octyl phthalate, n-nonylphenol, 3-pentadecyl phenylethyl ether, 2.
5-C sec ~ high boiling point solvents such as amyl phenyl butyl ether, monophenyl-di-O-lylorophenyl phosphate or fluoroparaffin, S and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol , diethylene glycol monoacetate, nitromethane, carbon tetrachloride,
Dissolved in a low boiling point solvent such as chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or sorbitan sesquioleate and sorbitan. It is mixed with an aqueous solution containing a nonionic surfactant such as monolauric acid ester and/or a lignophilic binder such as gelatin, and emulsified and dispersed using a high-speed rotary mixer, colloid mill, or ultrasonic dispersion device to form a silver halide emulsion. added.

In addition, the above DIR compound may be dispersed using a latex dispersion method.The latex dispersion method and its effects are as follows:
JP-A No. 49-74538, No. 51-59943, No. 54-32552 and Research Disclosure August 1976, NO, 14850, 77-79
It is written on the page.

Suitable latexes include styrene, acrylate,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N(2-(2-methyl-4- Homopolymers, cobosomers and terpolymers of monomers such as oxopentyl)) acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and the like.

The above DIR compounds are disclosed in U.S. Patent No. 3,227,554, U.S. Pat. 617, No. 291, No. 3,6:12.345, No. 3,928.041, No. 3. 'l: No. 13,500, 3.9311.99
No. 6, 3,951! , '193, same: l,! 16
No. 1,959.

No. 4,046,574, No. 4,052,213, No. 4,063,950, No. 4,095,984, No. 4
, No. 149,886, No. 4,234.678, British Patent No. 2,072,3+i3, No. 2,070,266,
Research Disclosure ztzza issue (1981
), JP-A No. 50-81144, JP-A No. 50-81145
No. 51-13239, No. 51-64927, No. 51-104825, No. 51-105819, No. 5
No. 2-65433, No. 52-82423, No. 52-1
No. 17627, No. 52-130327, No. 52-15
No. 4631.

No. 53-7232, No. 53-9116, No. 53-2
No. 9717, No. 53-70821, No. 53-1034
No. 72, No. 53-110529, No. 53-13533
No. 3, No. 53-143223, No. 54-13333, No. 54-49138, No. 54-114241, No. 57-35858, No. 54-145135, No. 55
-161237 No.9 56-114946, 57-
No. 154234, No. 57-56837 and patent application No. 1983
It can be synthesized by the method described in No. 44831, No. 57-45809, etc.

The DIR compound of the present invention can be added to a photosensitive silver halide emulsion layer and/or a non-photosensitive photographic constituent layer as described above, but is preferably contained in at least one of the silver halide emulsion layers. That's true. For example, when applied to a normal multilayer color photographic material having a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion, and a red-sensitive silver halide emulsion, it is contained in one or more of these layers. Just let it happen.

Each of the silver halide emulsion layers according to the present invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

As the above-mentioned couplers that can be used in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and it is also possible to use a diffusible dye-releasing type coupler or the like in combination with these couplers.

The yellow coupler may be a closed ketomethylene compound or a so-called two-equivalent type coupler.
〇-aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active point fluorine substituted coupler, active point chlorine or bromine substituted coupler Substituted coupler, active point -〇-
Sulfonyl substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.
, No. 265,505, No. 3,408,194, No. 3
．． No. 551,155, No. 3,582,322, No. 551,155, No. 3,582,322, No.
No. 3,725,072, No. 3,891,445, West German Patent No. 1,547,868, West German Application Publication No. 2,219,
No. 917, 2,261. : No. 161, 2,414.
No. 006, British Patent No. 1,425,020, Special Publication No. 1973
-10783, JP-A No. 47-26133, JP-A No. 48-
No. 73147, No. 51-102636, No. 50-63
No. 41, No. 50-123342, No. 50-13044
No. 2, No. 51-21827, No. 50-87650,
No. 52-82424, No. 52-115219, No. 5
Examples include those described in No. 8-95346.

Examples of magenta couplers used in the present invention include pyrazolone-based, pyrazolotriazole-based, birazolinobenzimitazole-based, and indasilone-based compounds. Similar to the yellow couplers, these magenta couplers are not 4-equivalent type couplers, but may also be 2-equivalent type couplers. Specific examples of magenta couplers include U.S. Pat. Nos. 2,600,788 and 2,983.
, No. 608, No. 3,0 to No. 2,65:1, No. 1, No. 1, 12
No. 7,269, 3. :lIl, No. 475, 3, 41
No. 9,391, No. 1.519,429, No. 3.558
．． : No. 119, 3,582. : No. 122, same :l
, No. 615,506, No. 3,834,908, No. 3,
No. 891,445, West German Patent No. 1,810.464, West German Patent Application (OL S') No. 2,408,665, No. 2,417,945, No. 2,418,959,
No. 2,424.467, Japanese Patent Publication No. 40-6031 2 Japanese Patent Publication No. 20826/1982, No. 52-58922, No. 4
No. 9-129538, No. 49-74027, No. 50-
No. 159336, No. 52-42121, No. 49-74
No. 028, No. 50-60233, No. 51-26541
No. 53-55122, patent application No. 55-110943
Examples include those listed in the No.

Further, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers are not only 4-equivalent type couplers like the yellow couplers, but may also be 2-equivalent type couplers. Specific examples of cyan couplers include US Pat. No. 2,359,929 and US Pat.
, No. 434,272, No. 2,474,293, No. 2,
No. 521,908, No. 2,895,826, No. 521,908, No. 2,895,826, Ibid.
No. 034,892, 3. : No. 111,476, same: l
, No. 458.315, No. 3,476.563, No. 458.315, No. 3,476.563, No.
No. 3,583,971, No. 3,591,383, No. 767.411, No. 3,772,002, No. 3.9:13,494, No. 4,004,929, West German patent application (OLS) 2,414,830
No. 2,454,329, Japanese Unexamined Patent Publication No. 48-59838
No. 51-26034, No. 48-5055, No. 5
No. 1-146827, No. 52-69624, No. 52-
No. 90932, No. 58-95346, Special Publication No. 1977-1
Examples include those described in No. 1572 and the like.

Couplers such as colored magenta or cyan couplers and polymer couplers may be used in combination in the silver halide emulsion layer of the present invention and other photographic constituent layers. Regarding the colored magenta or cyan coupler, a patent application filed in 1973 by the applicant
For polymer couplers, reference can be made to the description in Japanese Patent Application No. 1987-172151 filed by the present applicant.

The method of adding the above coupler that can be used in the present invention into the photographic constituent layer of the present invention has been conventionally used, and the amount of the above coupler added is not limited, or may be I x 1 per mole of silver.
Preferably 0-' to 5 mol, more preferably 1 x 1
0-'' to 5 x 10-'.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, such as anti-fogging agents, stabilizers, ultraviolet absorbers, etc. described in Research Disclosure No. 17643, It is possible to use a color stain inhibitor, a fluorescent whitening agent, a color image fading inhibitor, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, and the like.

In the silver halide color photographic light-sensitive material of the present invention, the woody colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, Any of cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide may be included.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include a glass plate, a polyester film such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, a polyamide film, a polycarbonate film, and a polystyrene film. The body is appropriately selected depending on the intended use of the photosensitive material.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

These structures? , ) 3 can similarly use hydrophilic colloids that can be used in the emulsion layer as described above, and various types of colloids that can be contained in the emulsion layer as described above can also be used as binders. Photographic additives may be included.

The processing method of the present invention can be applied to silver halide color photographic materials such as color negative films, color positive films, color reversal films for slides, color reversal films for movies, and color reversal films for TV.

[Effects of the Invention] According to the present invention, it is possible to provide a processing method in which the same sensitometric curve can be obtained by adjusting the color development time even at any temperature, and furthermore, it is possible to provide a processing method suitable for implementing the processing method. It is possible to provide a processing agent kit set having explanatory notes indicating the relationship between the color developer used, processing temperature, and processing time.

[Example] Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 A sample of a multilayer color photographic material was prepared by sequentially forming each layer having the composition shown below on a triacetylcellulose film support from the support side.

Sample (comparison) 1st layer/antihalation layer (HC-1) Black colloidal silver...0.22 Ultraviolet absorber (UV-1)
...0.20 colored coupler (CC-t)
...0.05 colored coupler (CM-2)
・-・0.05 high boiling point solvent (oil-1) ・・
・0.20 Gelatin ・・Archie, 4 2nd layer: Intermediate layer (IL-1) Ultraviolet absorber (UV-1) ・0.01 High boiling point solvent (oil-1) ・・0. O1 gelatin
...1.4 Third layer: Low sensitivity red-sensitive emulsion layer (IIL) Silver iodobromide emulsion (E, -1) Silver iodobromide emulsion (E, -2) Sensitizing dye (S-1) ・...1.0 ...0.5 ...2.5xlO~4 (mol/silver 1 mol) Sensitizing dye (S-2) ...2.5 x 10-' (dried mol/silver 1 mol) mol) Sensitizing dye (S-3)...0.5 x 10-' (mol/silver 1 mol) Cyan coupler (C-4)''...1.2 cyan coupler (C-2)'' ・・Tsukasa, 06 color cyan coupler (CC-1) ...0.05 DIR compound (D-1) High boiling point solvent (oil-1) Gelatin ...1.4 4th layer: High sensitivity red-sensitive emulsion Layer (RH) Silver iodobromide emulsion (E, -:l) Sensitizing dye (S-1)...0.5...o, ooz...2.0...2. Ox 10-' (mol/1 mol of silver) Sensitizing dye (S-2)...z, ox to-' (mol/1 mol of silver) Sensitizing dye (S-3) ・-0,1xtO- ' (Mole/1 mole of silver) Cyan coupler (C-1)" ...0.15 Cyan coupler (c-z)" ...mouth, O18 cyan coupler (C-3)" ...1.15 Colored cyan coupler (CG-1)...o, ots DIR compound (D-2) High boiling point solvent (oi 1-1) Gelatin 5th layer: Intermediate layer (IL-2) Gelatin 6th layer: Low sensitivity green Sensitive emulsion layer (GL) Silver iodobromide emulsion (E, -1) Sensitizing dye (S-4) ...0.05 ...0.5 ...1.4 ...0.5 ・...1.0...s, oxto-' (mol/1 mole of silver) Magenta coupler (X-1)''...0.5 Colored magenta coupler (CM-1)...0.05 DIR Compound (D-3) DIR compound (D-4) High boiling point solvent (oil-2) Gelatin 7th layer/intermediate layer (IL-3) Gelatin high boiling point solvent (oil-1) 8th layer: High sensitivity green Sensitizing emulsion layer (GH) Silver iodobromide emulsion (E,, -:l) Sensitizing dye (S-6) Sensitizing dye (S-7) Sensitizing dye (S-8) ...0.015 ・...0.020 ...0.5 ...1.0 ...0.8 ...0.2 ...1.3 ...1.5xlO (mol/1 mole of silver) ...・2.5 x 10-' (mol/1 mol of silver) -0.5x 10-' (mol/1 mol of silver) Magenta coupler Magenta coupler (M-2)''...0.06 (M-:l )''...0.18 Colored magenta coupler (CM-2)...0.05 DIR compound (D-3) High boiling point solvent (oil-:l)...0. Ol ・-・0.5 Gelatin 9th layer: Yellow filter layer Yellow colloid silver stain inhibitor (SC-1) High boiling point solvent (oil-:l) Gelatin 1st O layer: Low sensitivity blue-sensitive emulsion layer (BL) Iodine Silver bromide emulsion (
E, -1) Silver iodobromide emulsion (E, -2) Sensitizing dye (S-10) ...1.0 (YC) ...0.1 ...0.1 ...0. 1...0.8 11th layer (y-i)''...Tsukasa, 6 (Y-2)''...0, 12...0. Ol...0,15...1.0 Yellow coupler Yellow coupler DIR compound (D-2) High boiling point solvent (oil-3) Gelatin high sensitivity blue sensitive emulsion layer (8+1) Silver iodobromide emulsion (E, -4) Silver iodobromide emulsion (E, -1) Sensitizing dye (S-9) ...0.25 ...0.25 ...7. OX to-' (mol/silver 1 mol) ...0.50 ...0.20 ・-1, Ox 10-' (mol/silver 1 mole) #! Sensitive dye (S-10)...3.0XIO-4 (mol/1 mole of silver) Yellow coupler (Y-1)''...0.36 Yellow coupler (Y-2)''...0.06 High boiling point solvent (oi
lJ) - Tsukasa, 07 Gelatin
...1.1 12th layer: first protective layer (Pro-1) Fine grain silver iodobromide emulsion ...0.4 (average grain size 0.
08 lm, Agl 2 mol%) ultraviolet absorber (UV-
1) ・0.10 ultraviolet absorber (UV-2)
-0,05 high boiling point solvent (oil-1) -・
-0,1 High boiling point solvent (oil-4)...0.
1 formalin scavenger (Its-1)...0,
5 Formalin scavenger (Its-2)...0.2 Gelatin...1.0 13th layer: 2nd protective layer (Pro-2) Surfactant (Su-1) =-G, O05 alkali Matting agent soluble in
A[(knee 1) ...O, OQ5 magenta dye (^Ito1) ...0. Ol swell agent (WAX
-1) -0,04 gelatin
...0.8 In addition to the above composition, each layer contains a coating aid 5u-2, a dispersion aid 5u-3, a hardening agent) 1-1 and a) 2), a preservative Dil, and a stabilizer. 5tab-1 and antifoggant AF-1°AF-2 were added.

m-1 Average grain size 0.467zm, average silver iodide content 7.5%
Monodisperse surface low silver iodide containing emulsion m-2 Average grain size 0. : 12 gm, average silver iodide content 2.0% Monodisperse, uniform composition emulsion Ei-: 1 Average grain size 0.78 μm, average silver iodide content 6.0% Monodisperse, low iodide emulsion Silver-containing emulsion ε11-4 Tabular silver halide emulsion En+-1, Ea+- with an average grain size of 2.0 l, average silver iodide content of 8.0%, and a grain size 10 times the grain thickness: l and Era-4 are Japanese Patent Application Publication No. 1983
It is a silver iodobromide emulsion that has a multilayer structure adjusted with reference to the publications No. 138538 and No. 61-245151, and mainly consists of octahedrons.

In addition, for all of EIll-1 to Em-4, the average value of particle size/particle thickness was 1.0, and the width of the distribution per particle was 14%, 10%, and 12%, respectively.

Margin below S-9 S-! 0 Q Q Y-1 Cσ C,lf.

V-2
(CH-) -) tM(CH,)tsO3K 0 ■ il [)-4 CH u-1 Na0tS CC00CIIs(CrtCF2)sl
lC-COOC11, (CFtCFt)ffHH7 u-2 Na0sS CC00CJ+.

C1l.

C00C, If.

u AX-1 c-1 0H PF-2 H IC-1 I-1 IM-1 tab-1 Sample 1 prepared in this manner was exposed to wedge light using white light, and then subjected to the development process described below. went.

Processing process Processing time Processing temperature Color development
Table 1 25. :10.38℃ bleaching
90 seconds 30-37℃ constant
Wear 120 seconds 30-37℃ Wash with water 120 seconds 30-37℃
Stabilization 60 seconds 30-37℃ Drying 60 seconds 70℃
The concentration of the color developing agent in the color developing solution was changed from 0.01 [l1 ol/u to 0.25 mol/i using the following processing solution composition, and the color developing agent concentration was changed from 0.01 [l1 ol/u to 0.25 mol/i] at 25°C, 30°C, and 38°C.
The color development time was varied at 5 second intervals at a processing temperature of .degree.

The composition of the treatment liquid used is as follows.

[Color developer] Potassium carbonate 40g Sodium bicarbonate 2.5g Potassium sulfite 4g Sodium bromide
1. :1g potassium iodide
1.2mg hydroxylamine sulfate fp 2.5g sodium chloride
0,6g4-amino-3-methyl-N-
Ethyl-N-(β-hydroxylethyl)aniline sulfate Listed in Table 1 Add 1.2 g of potassium hydroxide to make up to 100 ml of water, and adjust the pH to 10 using potassium hydroxide or 50% sulfuric acid.
Adjust to 06.

[Bleach solution 1.3-Propylenediaminetetraacetic acid ferric ammonium salt 25g ethylenecyaminetetraacetic acid rpJ2 iron ammonium salt 25g ammonium bromide 150g Add water to make 1M
and adjust the pH to 5.2 using aqueous ammonia or glacial acetic acid.

[Fixer] Add 250 g of ammonium thiosulfate and 20 g of ammonium sulfite to make 1 liter, and adjust the pH to 6.8 using acetic acid and aqueous ammonia.

[Stabilizing solution] Formaldehyde (37% solution): 1mu Emulgen 810 2+au Add water to make ti, adjust pH with ammonia water and 50% sulfur
Adjusted to 7.0.

The sensitometric curve of the developed sample was measured, and the gamma value and minimum density (D, in) in the interval from the density of fog + 0.1 to the exposure range E-1,5 were determined as blue (B), clean (
G), red (R), and the three-color measurements were obtained.
Color development processing time, other gamma values, and Dmi when the gamma value measured in clean light is 0.55. The details are shown in Table 1.

Table 1 below shows the gamma values of B, G, and R and D+ll+ when the temperature is changed from 25°C to 130°C to 35°C. It is preferable if there is no difference in .

As is clear from Table 1, the color developing agent concentration, 2
At 10-2 mol/u or more, the gamma value, D□, depends on the color development temperature. It turns out that the difference is small and very desirable.

Example 2 In Example 1, the source strength of 5 color developing agents was 0.015 mo.
l/4 and 0.05mo! The same experiment as in Example 1 was carried out for the two points of /4 using a color developer containing the inhibitor shown in Table 2 (compounds described in the specification) and the color development temperature of 30°C and 38°C. I did it.

The results are shown in Table 2.

As is clear from Table 2, when an inhibitor is added, especially D1□. It can be seen that the fluctuation is small and it is very effective.

Example 3 Instead of adding an inhibitor in Example 2, an experiment was conducted in which the pH value of the color developing solution was increased (pH was changed by KOJl).

The results are shown in Table 3.

As is clear from Table 3, increasing the pH value for color development makes it possible to speed up the color development time and reduces the difference in sensitometry due to temperature differences, which proves to be effective.

Example 4 The color negative produced in Example 1 was designated as A.

In the color negative production method shown in Example 1, DIR
No compound was added, the amount of water added was reduced by 20%, and the amount of coupler was increased by 15% to make a color negative for sensitometric adjustment.

Next, the core/shell emulsions of El-1 to E7-4 and the T-grain emulsions of halogenated [1] were changed to simply uniform composition emulsions, and sensitometry iI8! The particle size was reduced by 15% to improve the
A color negative with the same amount of water added was designated as C.

The color negative produced by taking both BC measures was designated as D.

Color negatives A to D were developed in the same manner as the control development in Example 2, and the results are shown in Table 4.

As is clear from Table 4, the invention / is [lIR compound,
A, B using core/shell emulsion, tabular grain emulsion,
When color negatives C are processed, it can be seen that the effect of the present invention is more effective when compared with unused color negatives D.

Example 5 2-45+eg1l instead of the inhibitor of Example 2.

7-50. In+g/4, Z-710mg/dan, Z-1
820ag/l, Z-200, 4mg/1. Z-2
120II1g/text, Z-275mg/JL.

1-28 0.5mg/41, Z-305mg/l, Z
-395mg/u.

The same experiment was conducted using Z-420, 4B/i, and Z-650, 1 mg/l.

The results were similarly favorable.

Example 6 The following color developer kit was prepared.

Bart A Potassium carbonate 60g Sodium sulfite 3g 4-Diethylenetriaminepentaacetic acid 5Na salt 3gZ-5o
,zg Bart B 4-Amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)aniline sulfate 15g Par 1-A,B
Both are powder kits.

It was placed in a thermostat at 50°C for one week to perform a forced deterioration test over time, and Virt A and B were dissolved in water to form 11.

After exposure of the color negative prepared in Example 1, the color developing solution was heated at 25°C for 7 minutes, 3 minutes (1'C, 3 minutes 40 seconds, and 38 degrees Celsius).
℃ 1 minute 50 seconds, the treatment process and treatment solution of the example process (
(others) was used for development. The obtained developed negative was printed on color vapor under the same conditions, and as a result, the color vapor finish remained constant even when the color development temperature was different, which was a very favorable result.

In addition, we finished Bart A to 200 m JJ with water and Bart B to 100 m JJ with water added with 1 g of potassium sulfite, and put them in a bed bottle after forced deterioration and conducted a similar experiment, which was also very favorable. There was a result.

[Brief explanation of the drawing]

Fig. 1 is a front view showing an example of the explanatory text of the processing agent kit set according to the present invention.

Claims (1)

[Claims] 1. In a method of processing a silver halide color negative film with a color developer after exposure, at least 2.0 x 10 p-phenylenediamine color developing agents having a water-soluble group are added per liter of the color developer. ^-^ Contains 2 moles or more, and is processed by changing the color development time depending on the processing temperature of the color developer,
A method for processing a silver halide color negative film, characterized in that the processing time is within 6 minutes when the processing temperature of the color developing solution is 30°C. 2. At least 2.0 x 10 p-phenylenediamine color developer main ingredients having a water-soluble group per liter of color developer.
^-^ It is possible to have a color developer containing 2 moles or more and a color developer using the color developer at two or more processing temperatures, and the processing time when the color development processing temperature is 30°C. A processing agent kit set for silver halide color negative film, characterized by having an explanatory note explaining that processing can be performed within 6 minutes.