JPS62275249A - Color image forming method - Google Patents

Abstract

PURPOSE:To form high color development density in a short time even in the case of a color developing solution containing no benzyl alcohol by developing a photographic sensitive material containing flat silver halide grains, after imagewise exposure, within a prescribed time with a color developing solution containing substantially no benzyl alcohol. CONSTITUTION:The silver halide color photographic sensitive material is provided on a reflective support with an least one silver halide emulsion layer containing the flat grains of silver chlorobromide and/or iodobromide substantially no silver iodide, and each of the grains amounting to >=50% of the projected areas of the total grains has an aspect ratio of >=5, and such flat grains have high color developing performance even in the color developing solution, and it is preferred that the grains each having a grain diameter of 0.3-2.0mum, and an average grain diameter to average grain thickness ratio of 5-8 amount to >=85% of the total projected areas of the total silver halide grains.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention <Industrial Application Field> The present invention relates to a novel color image forming method that improves color reproducibility, and more specifically relates to a method of forming a color image that causes less environmental pollution. This invention relates to a color image forming method that enables rapid processing.

<Prior art> In order to form a color photographic image, three colors of photographic power, yellow and magenta, are contained in the photosensitive layer, and after exposure, a color developer containing a color developing agent is processed. do. In this process, the oxidized product of the aromatic primary amine undergoes a coupling reaction with the coupler to give a colored dye, but in this case, it is necessary to give as high a color density as possible within the limited development time. It is.

To obtain high color density, use couplers with as high a coupling rate as possible, or
This is usually achieved by using a silver halide emulsion with a high amount of developed silver per unit coated amount or by using a color developing solution with a high ring rate.

In addition, in order to obtain good color reproducibility with color reflective light-sensitive materials, it is necessary that the spectral sensitivities between each light-sensitive layer be clearly separated. Separation in the blue region, where the two overlap, is an important issue.

Regarding this point, the sensitivity is usually increased by making the silver halide grain size of the blue-sensitive layer larger than that of other layers, and by making the sensitivity of the blue-sensitive layer different from the green and red-sensitive Iφ. Usually achieved.

<Problems to be Solved by the Present Invention> In order to improve color reproducibility and increase the photosensitivity of the blue-sensitive layer in the blue-sensitive region, increasing the particle size is a commonly used means. , this will slow down the development speed, and this alone cannot achieve the purpose of the invention.

In order to speed up the development of a silver halide emulsion, it is easy to think of increasing the silver chloride content of the silver halide, but if the silver chloride content increases, sensitivity decreases and fog occurs. In addition, in order to increase the amount of active silver, it is possible to increase the above-mentioned silver chloride content or to strengthen chemical sensitization, but in this case too, fogging will occur. ...Reducing the grain size of the silver chloride emulsion is also a means of speeding up development, but it has the fatal drawback of decreasing sensitivity.The method using silver chloride emulsion , for example, JP-A-Shoj1
-7!3μ! Same issue! ? -232314λ and 6
Although it is described in No. 0-/R/μO, it causes high fog and is not suitable for practical use.

It is also known that, in addition to increasing the silver chloride content, the flatness can be improved by making the grain shape tabular. For example, in JP-A No. 11-1983/1/1999, it has opposing parallel (///) main surfaces and has an uncut surface of 0.3 μm.
It has been proposed to use a tabular silver chlorobromide emulsion having a thickness, a diameter of 0.6 μm or more, an average aspect ratio of 7 or more, and a silver chloride content of up to μOmo 1%, and it is said that it has a high development speed change. Shown as an example in liquid form. However, there is no specific description of the use of this invention in the family tree, nor is there any mention of its use as a means to solve the problems described below.

On the other hand, various measures have been conventionally taken regarding color developing solutions to speed up development. Among these, various additives have been studied in order to accelerate the penetration of the color developing agent into the color coupler-dispersed oil droplets and promote color development.In particular, benzyl alcohol? The method of speeding up color development compared to using a color development solution is currently widely used in the processing of color photographic materials, especially color photosensitive materials, because it has a great effect of promoting color development.

However, when benzyl alcohol is used, diethylene glycol, triethylene glycol, alkanolamine, etc. are required as a solvent due to its low water solubility. However, since these compounds, including benzyl alcohol, have a high BOD and CODb'' which are polluting fish, it is preferable to remove benzyl alcohol for the purpose of reducing the pollution load.

Furthermore, even if this solvent is used, it takes time to understand benzyl alcohol, so it is better not to use benzyl alcohol for the purpose of reducing the volume of liquid preparation.

Furthermore, if benzyl alcohol is brought into the post-baking bleach bath or bleach-fixing bath for 1 hour, it causes the formation of leuco dye of cyan dye, which causes a decrease in color depth IW. Furthermore, since the washing-out rate of the developer components is delayed, the image storage stability of the processed photosensitive pigment may be adversely affected.

Therefore, also for the above reasons, it is preferable not to use benzyl alcohol.

Conventionally, it was common for color development to be processed in 3 to ≠ minutes, but with the recent shortening of finishing delivery times and the reduction of laboratory work, there is a desire to shorten processing times. Ta.

However, when benzyl alcohol, which is a color development accelerator, is removed and the current fJ time is shortened, significant color development occurs. Decrease in J degree? It is inevitable that this will happen.

In order to solve this problem, various color development acceleration methods (for example, U.S. Patent No. 70, No. 2, J/!,
/Hiroshi No. 7, same 2. ≠Riotsu, Ri03, same u, 30u
, No. 225, 14.03! r, No. 076, @J Hiroshi,
//Ri, ≠6λ, British patent/, ≠3o, Riyr, J
ul/, 1Ajj, 'AI No. 3, Tokukai Sho! J
-/j13/ issue, same! -62≠jo issue, same! ! -Aλ
IA! r1, same jj-ot2tAj2, same! -62
≠! No. 3, Special Public Sho J'/-/24-λ, same! ! - Section 7
Even when the compound described in No. 72r was used in combination, sufficient color density could not be obtained.

A method of incorporating 3-pyrazolidones (for example, Japanese Patent Application Laid-open No. 1973
−． 24JJr issue, same 1pO-/! ruul A, same t
Even if the method described in No. o-isrtA4ct is used, there is a drawback that I-blinking occurs, which causes the sensitivity to decrease over time.

Also, a method of incorporating a color developing drug (for example, U.S. Patent No. 37
7ri μri No. 2, same! JIA Kojyo No. 2, Hiroko 33! 2
No. 7, JP-A-54-623! No., jA-/l/33, j7-4713/, j7-43j&! Even if the method described in No. 1, etc. is used, it is not an appropriate method because it has the drawbacks that the color development phenomenon is delayed and capri is generated.

As described above, no method has been found for obtaining sufficient color images in a short period of time using a color developing solution that does not substantially contain benzyl alcohol.

Therefore, a first object of the present invention is to provide a color image forming method that provides high color density in a short time even when using a color developer that does not substantially contain benzyl alcohol.

A second object of the present invention is to provide a color photographic material that exhibits less capri and is rapidly developed.

A third object of the present invention is to provide a color photosensitive material with improved color reproducibility.

The purpose of the present invention is to obtain color photographic paper with less environmental pollution (and improved color reproducibility through quick practical processing).
At least 50% of the total projected area of silver chlorobromide and/or silver bromide grains substantially free of all silver iodide on the reflective support.
% or more contains tabular grains with an average aspect ratio of j or more.
- A photographic light-sensitive material coated with at least one silver halide photographic emulsion layer is developed within 2 minutes and 30 seconds with a color developing solution that does not substantially contain benzyl alcohol after exposure. This was simultaneously achieved by a color image forming method characterized by the following.

In the present invention, "substantially free of benzyl alcohol" means that the benzyl alcohol concentration in the color developer solution is 0.
．． less than 1 ml/1, preferably all (meaning not containing).

aspect ratio! The tabular silver halide grains described above unexpectedly had high color development even in a color developer. It is known that in color development, unlike black and white development, it takes a long time for the /@/ silver halide grains themselves to develop, and this is the rate-determining step.

It was an unexpected effect that flattening the grains accelerates the color development process with the properties described above.Increasing the aspect ratio has the effect of speeding up the development. However, the solubility of silver halide in the developing solution increases, and this tendency is even more pronounced with silver chlorobromide, which is commonly used in color reflective materials.Aspect ratio of 73 or more When this happens, the dependence on processing factors, which is thought to be due to this property, increases (or the capri increases), which is undesirable.

It is well known that it is effective to increase the silver chloride content in order to speed up the development speed, but this is not a preferred method because it usually causes fogging, and in color photographic paper systems, Not normally used.

Tabular emulsions were also unexpectedly found to exhibit less capri formation with increasing silver chloride content. Therefore, in tabular emulsions, silver chloride milk 41 having a high silver chloride content, which is usually difficult to use, can be used, and the effect of accelerating color development can also be obtained.

It is known that increasing the aspect ratio makes it possible to obtain high color sensitization.

The advantage of good color sensitization is that high sensitivity can usually be obtained with a small particle size, so in terms of photographic performance, for example, improvement of graininess, constant development is required for black and white photosensitive materials such as silver images, etc. It is known that the blackening density is high relative to the amount of silver.

The present inventors have discovered that in the color photographic paper system, the above-mentioned points are not an advantage at all, and the great advantage is the low intrinsic sensitivity with respect to the high color sensitization.

In the case of color photographic paper, as mentioned above.

Increase the sensitivity difference between the blue sensitive layer and the green and red sensitive layers in the blue region (
This relatively low inherent sensitivity of the green and red sensitive layers is particularly effective in this color photographic paper system.

A common method for providing sensitivity differences in the blue region is to arrange the blue-sensitive layer as the topmost layer (the layer that is faster than the support), and to provide a layer of yellow filter between the green- and red-sensitive layers. (Are known.

However, in color reflective light-sensitive materials, the emulsion layer has a
Since the original light is reflected from the white reflective support at least once and is directed toward the emulsion layer from the support side, each emulsion layer receives the same amount of light as if it had been exposed at least twice. Providing a single yellow filter cannot be used because the amount of light that reaches the blue sensitive layer is substantially reduced to less than 2, resulting in an apparently significant decrease in sensitivity.

The present inventors have found that by increasing the amount of light absorption in the blue region of the blue-sensitive layer, the color reproducibility of color reflective materials under the above-mentioned special circumstances is improved. A tabular emulsion having a 100% sensitizing dye can adsorb a larger amount of sensitizing dye, and therefore exhibits extremely high light absorption. An emulsion that has a high aspect ratio in the blue-sensitive layer and has a large number of sensitizing dyes adsorbed exhibits high light absorption in the blue region, and as a result, the amount of light reaching the green and red-sensitive layers is reduced.
It has been found that the effect of reducing the apparent sensitivity in the halo color range of the green and red sensitive layers can be obtained. This effect was further enhanced by providing a blue-sensitive layer as the topmost layer.

It was also observed that by installing a blue-sensitive layer on the top layer, the speed of color development was accelerated.

As mentioned above, it has been found that tabular emulsions with an aspect ratio of 3 or more exhibit high color development in a color developer and have improved color reproducibility. It is clear that it is also effective in the photosensitive layer, but
It is particularly preferable to use it in the blue-sensitive layer (and it is more preferable to use it in all layers).

In the silver halide emulsion used in the present invention, tabular grains having an average aspect ratio of 5 or more account for a small amount (or !0%) of the total projected area of the silver halide grains. "Ratio" refers to the ratio of the diameter to the thickness of the particle.

The "diameter" of a grain refers to the diameter of a circle having an area equal to the projected area of the grain when the emulsion grain is observed under a microscope or an electron microscope. From a shaded electron micrograph of an emulsion sample, the thickness and diameter of each grain can be measured, the aspect ratio of each tabular grain can be calculated, and the aspect ratio of all tabular grains in the sample can be calculated. Aspect ratios can be averaged to obtain an average aspect ratio. Average aspect ratio! The projected areas of the above tabular grains are integrated, and the projected areas of the remaining silver halogenated grains in the micrograph are integrated separately. From these two integrated values, it is determined that the tabular grains are halogenated. It is possible to calculate the proportion of the projected area of the entire silver coffin.

The diameter of the flat plate-shaped silver halogenide coffin is O0/-1
0a, preferably 0.2 to r, 0μ, particularly preferably 0.3 to 6. It is Qμ. The thickness of the particles is preferably 0.3 μm or less.

The grain thickness is expressed as the distance between two parallel planes constituting a tabular silver halide grain.

In the present invention, more preferred tabular silver halide grains have a cryodiameter of 0024 m or more and 3.0 μm or less,
The particle thickness is 0.3 μm or less, and the average diameter/average thickness is j or more/j or less.

More preferably, the particle diameter is 0.3 μm or more.

The average diameter/average thickness is less than 0μm! All of the grains with a size greater than or equal to r or less are the total projected area of the silver halide grains? ! This is the case for silver halide photographic emulsions that account for more than

The size distribution of the tabular silver halide grains used in the present invention may be narrow (or wide), but it is preferably a monodispersed emulsion, and the grain size distribution, which represents the degree of nest dispersion, is statistically The ratio of the standard deviation (S) to the average particle size (d) (S
/d) is preferably 0.23 or less, more preferably 0
．． 2 or less, more preferably Q, /yo or less.

The silver halide emulsion used in the present invention consists of silver chlorobromide and/or silver bromide that does not substantially contain silver iodide,
Preferably, the emulsion is a silver chlorobromide emulsion containing silver chloride from λ molts to O molts. Further, "substantially not containing silver iodide" means that the content is λ morti or less, preferably completely (not containing).

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may have a uniform phase throughout the grain. Moreover, they may be mixed. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The tabular silver halide emulsion used in the present invention is Cu
gnac, Chateau's report, and Duffin's ``
Chemistry of Photographic Emulsions J
lsion ChemistryJ (Focal
Published by Press + New York / 1966) 66
Pages ~7λ, and A, P, H, Trivelli, W.
Edited by F. Sm1th [Photo Magazine J (Photo, J
own ) J' 0 (/ri μO year) xrs
Although it is written on the page, Tokukai Sho! r-//3927,
Same as 1-//3'? 2r issue, same! It can be easily prepared by referring to the method described in ♂-727 Octopus No. 7.

For example, in an atmosphere with a relatively high pAg value with pBr of /, 3 or less, seed crystals containing tabular grains in an amount of UO% or more by weight are formed, and while maintaining the same pBr, silver and... It can be obtained by growing the crystals while adding it. During this grain growth process, it is desirable to add a silver and...logen solution to prevent the generation of new crystal nuclei.

Tabular...The size of silver halide grains is determined by temperature control, selection of solvent type and quality, silver salt used during grain growth, and...
It can be adjusted by controlling the rate of addition of the halides.

When producing the tabular silver halogenide grains of the present invention, if necessary, a silver halogenide bowing agent may be used to improve grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution, The growth rate of particles can be controlled.

The amount of the solvent used is preferably in the range of 10 to 7.0% by weight, particularly preferably in the range of 10 to 10% by weight of the reaction solution.

In the present invention, as the amount of solvent used increases, the particle size distribution becomes monodisperse and the growth rate can be accelerated, but the thickness of the particles also tends to increase as the amount of solvent used increases.

In the present invention, known silver halide G agents can be used. Examples of frequently used silver halide solvents include ammonia, thioethers, thioureas, thiocyanate salts, thiazolinthiones, and the like. Regarding thioethers, reference can be made to U.S. Patent No. 3.27/, /j7, U.S. Pat. Japanese Patent Publication No. 53-42≠Or,
U.S. Pat.
r, jJu No. 3,320. Regarding Otori, thiazolinthione, please refer to JP-A-J3-/Ko-IA3/? You can refer to each issue.

In the process of forming or physically ripening silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may coexist. (1° When producing the tabular silver halide grains used in the present invention, a silver salt solution (for example, A
g ~ 03 water bath solution) and...rogenide solution (e.g. KBr
A method of increasing the addition rate, addition amount, and addition concentration of the aqueous solution is preferably used.

Regarding these methods, see, for example, British Patent No. 1゜33j
, Riyo No. 2, U.S. Patent No. 3.6!0.767, U.S. Patent No. 3
, 67λl 00, I Tsukasa μ1.2 Hiro-2≠≠j,
Tokukai Shoj! -/Hiroshi, 23λri issue, same! -/! l1lj
You can refer to the description of the number etc.

After grain formation, silver halide emulsions are usually subjected to physical ripening,
It is desalted and chemically aged before being used in cold blood. To remove soluble silver salts from the emulsion after physical ripening, VC may be subjected to Nordel water washing, fluorolysis precipitation, ultraleakage, etc.

The tabular silver halide grains of the present invention can be chemically sensitized if necessary.

That is, sulfur sensitization using a sulfur-containing compound that can react with active gelatin or silver (for example, thiosulfate, thiourine compounds, mercapto compounds, logenine); reducing substance 3i1
t (e.g., stannous salts, amines, and drazine derivatives,
Reduction sensitization method using formamidine sulfinic acid, 7 run compound); noble metal compound (for example, total complex salt, pt
, rr, complex salts of metals of group V11I of the periodic table with Pd, Rh, Fe, etc.)? The noble metal sensitization methods used can be used alone or in combination.

Among the above chemical sensitizations, sulfur sensitization alone is particularly preferred.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes it possible to clarify the dye image formed in the silver halide emulsion layer. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. It will be done. For example, ・5 lighter paper,
Polyethylene coated paper, polypropylene synthetic paper, transparent support with a reflective layer or a reflective material, such as glass plate, polyester film of polyvinyl terephthalate, cellulose triacetate or cellulose nitrate, polyamide film , polycarbonate film, polystyrene film, etc., and these supports can be appropriately selected depending on the purpose of use.

Next, the processing step (IIII image forming step) in the present invention will be described.

The color development process in the present invention has a short processing time of 2 minutes and 30 seconds or less. The preferred treatment time is 30 seconds to 2 minutes and 30 seconds. The processing time herein refers to the time from when the photosensitive material comes into contact with the color developer to when it comes into contact with the water bath, and includes the transit time.

The color developing solution used in the color development process of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-
Phenyl diamine compounds are preferably used, typical examples of which include 3-methyl-Hiro-Abanoh, N-diethylaniline, 3-methyl-μm aminoh, ethylh, β-hydrofluethylaniline, and 3-methyl. −≠−
Amino-ethyl-1β-methanesulfonamidoethylaniline, 3-methyl-≠-amino-12-methyl-β-methogyaethylaniline, sulfate, hydrochloride, phosphate or p-toluene Examples include sulfonate, tetraphenylborate, p-(t-octyl)benzenesulfonate, and the like.

Examples of aminophenol derivatives include 0-aminophenol, p-aminophenol, ψ-abanocormethylphenol, no-amino-3-methylphenol, 2-okino-3-amino/, lA-dimethylbenzene, and the like. .

In addition, "Photographic Processing Chemistry" by F. A. Meson, Focal Press (
/ri 66) (L, F, A.

Mason, “Photographic Process
ssingChemistry'', Focal Pre
ss), pp. 22A-222, U.S. Pat.
R No. 2゜! Octopus, No. 36μ, Tokukai Sho≠♂- Kou 23
Those described in No. 3 may also be used. λ as required
It is also possible to use a combination of more than one type of color developing agent.

The processing temperature of the color developer in the present invention is 300~j
0°C is preferred, more preferably 320C-≠2°C
It is.

Further, as the development accelerator, various compounds may be used, except that they do not substantially contain benzyl alcohol. For example, US Patent Yu, A (Ar, No. 40ψ, Special Publication Sho≠Hiroshi-2!
No. 03, U.S. Patent J, /7/.

Various birimidium compounds typified by λHong No. 7 and other karaonic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, Japanese Patent Publication No. 1L-230≠, U.S. Patent U, j3
3. No. 220, No. λ, No. 131゜rJx, No. 220, No. 131゜rJx, No. 220, No.
, No. 970, polyethylene V described in J, J77, No. /27
Nonionic compounds such as glycol and its derivatives, polythioethers, US Patent 3. Examples include the thio2-based compounds described in λO/, 2μλ, and other compounds described in JP-A No. 10-220JtAII.

In addition, in short-time development processing as in the present invention,
It is not just a means of accelerating development, but also a means of accelerating development.
- Prevention technology will become an important electrification charge. Preferred antifoggants used in the present invention include alkali metal chlorides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants.

Examples of organic anti-capri agents include benzotriazole, A-nitrone compound l-7''-A/, j-nitroinoindazole, j-methylbenzotriazole, j
-Nitrogen-containing heterocyclic compounds such as ditropensotriazole, y-chloro-benzotriazole, 2-thiazolyl-benzimidazole, cortiazolylmethyl-benzimidazole, hydroquinazaindolizine, and/-phenyl-y-mercapto. mercapto [mono-substituted heterocyclic compounds such as tetrazole, 2-mercaptobenzimidazole, comelcabutobenzothiazole, and mercapto r? such as thiosalicylic acid; Other aromatic compounds can be used. Particularly preferred are rogogenides. These antifoggants may be extracted from the color light-sensitive material during processing and may be accumulated in the color developing material.

In addition, the color components of the present invention include pH buffering agents such as alkali metal carbonates, borates or phosphates: hydroquinolamine, triethanolamine, OLS No. 2A Co. 27. Preservatives such as compounds described in No. 0, sulfites or bisulfites; organic solvents such as diethyl glycol; dye-forming couplers;
Competitive couplers; nucleating aFl such as sodium boron hydride; auxiliary compounds such as /-722-3-pyrazolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid,
Nitrilotriacetic acid, chlorohexanediaminetetraacetic acid, ibanoniacetic acid, hehydroxymethylethylenediazuntriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and JP-A-Shojl-/Risrhiro! Research Disclosure
aminophosphonic acids such as aminotris (methylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylene phosphonic acid), Tokukai Shoyo λ-10+2724, same!3-Hiroshi 273Q, same!Hiroshi-1λ//core issue, sameo j-tAOλHiro, reference s-HiroOλj, same!!-/262Hir/ Same number, 1,69
Yo 5, same yo 16! Research Disclosure
It can contain a chelating agent such as the phosphonocarboxylic acid described in relA/r/No. 70 (/"?7P year! month).

Further, the color development bath may be divided into λ or more parts as necessary, and the color development replenisher may be replenished from the first bath or the last bath, thereby shortening the development time and reducing the amount of replenishment.

After color development...Silver halide color photosensitive materials are usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment (bleaching and fixing) or may be carried out separately. Examples of bleaching agents include iron (1), cobalt (lI[),
Compounds of polyvalent metals such as chromium (■) and copper (II), peracids, quinones, and nitrone compounds are used. For example, ferricyanide, dichromate, organic complex salts of iron(III) or cobalt(Ill), aminopolycarbonates such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 113-diamino-λ-propaturtetraacetic acid, etc. Complex salts of citric acids or organic acids such as citric acid, tartaric acid, and malic acid; persulfates, manganates; nitrosophenols, and the like can be used.

Among these, potassium ferricyanide, sodium ethylenediaminetetraacetate ([[), ammonium ethylenediaminetetraacetate (■)], iron triethylenetetraminepentaacetate (l [[) ammonium], and persulfates are particularly useful. Ethylenediaminetetraacetic acid iron(III) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

Further, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution, if necessary. For example, in addition to bromide ion and iodide ion, U.S. Patent No. 3,704,561,
T issue, same≠Turcoro! ! No. 6, Japanese Patent Publication No. 63-3273j
No. 13-36233 and same! ! Thiourea-based compounds as shown in the specification of -370/6, or JP-A-Sho! 3-/Ko Hirohiro 2≠ issue, same! 3-Tayo Otsu No. 37, Dojo 3-Yo 713/No., Dojo 13-327jA, Dojo! 3-6
Yo 732, same! ≠−! No. 2!3≠ and U.S. Patent No. 3.
lrri3. ! ! Thiol-based compounds as shown in No. R Specification A, etc., or JP-A-Akihirota! ri No. 11, same jO-
/≠0/2nd issue, same! 3-21'1A21. No. 3
-/≠/lko3, samej3-70hiro-32, same! Hiroshi
Heterocyclic compounds described in JP-A No. 3!727, etc., or JP-A-52-20132, jj-2rOt', and JP-A-20132! ! -24106 specification, etc., or the thioether compound described in the specification, etc.
The quaternary amines described in the specification of No.
Compounds such as thiocarbamoyl described in the specification of ≠23 may also be used.

Examples of the fixing agent include thiosulfate, thio/anate, thioether compounds, thioureas, and a large amount of iodide '4, but thiosulfate is generally used. As a preservative for bleach constant Mq or constant M solution, sulfite, bisulfite or carbonyl bisulfite adducts are preferred.

After the bleach-fixing process and the fixing process, a washing process is usually performed. Various known compounds may be added to the water washing process for the purpose of preventing precipitation and saving water. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid to prevent precipitation, disinfectants and anti-bacterial 41 to prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum. A hardening agent typified by salt or a surfactant for preventing drying load and unevenness may be added as necessary. Or L.E. West (L
, E., West), Photographer Science and Engineering, (Photo.

Sci, and Eng,), Volume 2, No. 2, (/
Compounds described in Riotori et al. may be added. Particularly effective are chelate cutting and addition of anti-piping agents. It is also possible to save water by using a multistage (for example, 2 to ! stages) countercurrent method in the water washing process.

Also, after or instead of the water washing process, JP-A-7-
A multi-stage rotary first-flow stabilization treatment process as described in No. 46 Ko No. 3 may also be carried out. In the case of this step, a countercurrent column with a λ tank is required. Various compounds are added to this stabilizing bath for the purpose of stabilizing the image.

For example, buffers for adjusting the membrane p)l (e.g. borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids) acids, polycarboxylic acids, etc.) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (Proxel, isothiazolone, ≠-thiazolylbenzimidazole, halogenated phenol benzotriazoles, etc.), surfactants, fluorescent brighteners, hardeners, etc. may be added.

In addition, ammonium chloride,
It is also possible to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosuccinate, etc. The blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention each have their color sensitivity enhanced by a methine dye or the like. It has been spectrally sensitized so that it has The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, melonanine dyes and complex mero-7anine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, ibadazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus , benzimidazole cough, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

Melonanine dyes or complex merocyanine dyes include pyrazoline-yone nuclei, thiohydantoin nuclei, corchioxazolidine-co, Hiro-dione nuclei, thiazolidine-λ, ≠-dione nuclei, rhodanine nuclei, and thiobarbyl as nuclei having a ketomethylene structure. J-4 membered heteroartic ring nuclei such as acid nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is the US Patent Co., Ltd.

77,22 ri No. 3,327.0 Otsu O, 3, j
2λ, 0J2 No., J, 127.4 Hiroshi/No., J, A
/7.25'j issue, same J, A, 2g, 2.44c issue, same 3. tti,, uro issue, same J, l, 72. ryr issue,
3.679, '421, Ibid. j, 7 (7J.

No. 377, No. 3, 76, No. 30/, No. 3. ♂／a,t
, No. o, J, 137, No. r12, No. 4'.

No. 026.707, British Time FF/, 344! ,
2r1 issue, same / ,! No. 07.103, Special Public Akihiro 3-
Hiro 236, same 13-/237! No., Tokukai Akira! λ-I1
0 AI? No. J2-10 Tata No. 2J.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

To spectrally sensitize silver halide emulsions with these sensitizing dyes, generally known methods can be used. That is, the sensitizing dyes are mixed with a suitable bath medium (methanol, ethanol, ethyl acetate, etc.). This is done by dissolving G in a suitable concentration and adding it to a silver halide emulsion.The above solution is added at any step during the preparation of a silver halide emulsion.For example:・Stabilizers and anti-capri agents can be used at any stage during the formation of silver fluoride emulsion grains, after formation, before chemical ripening, during chemical ripening, after the completion of chemical ripening, before preparing a coating liquid, or during the preparation of a coating liquid. The order in which the emulsions are added does not matter, but it is preferable that they be added before coating Q or preparation.Especially when using a blend of multiple emulsions having substantially the same color sensitivity, these Preferably, it is added before blending the emulsion.

It is preferable that the color coupler incorporated in the light-sensitive material has diffusion resistance by having a ballast or being made into a polymer. The amount of coated silver can be reduced by using a four-dant color coupler in which the coupling active position is a hydrogen atom, and a two-dt color coupler substituted with a leaving group. Couplers in which the coloring dye has adequate diffusivity, colorless couplers, or DIR couplers that release development inhibitors or development promoters upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected type unruly acetate coupler. A specific example is U.S. Patent No. 2,4t
No. 07,270, same No. 2. ! 7j, No. 0!7 and No. 3.27. ! , 50% issue, etc. The use of two-handed yellow couplers is preferred for the present invention, as described in U.S. Patent No. 3. Hiro01,/? U No. 3,447,121
No. 31, 33. Yo07 and same No. tA, θ22
The oxygen atom separation type yellow coupler described in ゜620, etc. or the Tokko Sho 1! -/(No. 77J, U.S. Patent No. ≠0/, 712, U.S. Patent No. ≠, 32A, 0.
1tl-No., RD/rO,! FJ (/ri71? μ month)
, British Patent No. 1. lt2! , 0λO, West German Application Publication No. 1, Co/? , No. 17, No. 2.26/, No. 361, No. 2.329, No. j17 and No. λ.

A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 33,112. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, and -10,000 α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected couplers of the ingzolone type or cyanoacetyl type, preferably pyrazoloazole type couplers such as pyrazolone type or pyrazolotriazoles. ! -Pyrazolone couplers are preferably those in which the 3-position is substituted with an arylamino group or an acylamino group in terms of the hue of the coloring dye and the mass point of the coloring a+, and representative examples thereof include U.S. Pat. , No. 2゜3≠j, No. 703, No. 600,711, No. u, Pol, No. 173, No. 3,01,2,43
No. 3, same 1f, 3. /! λ,? It is described in No. 26 and the same No. 3゜3t, oir, etc. As a leaving group for a two-equivalent pyrazolone coupler, U.S. Pat.
310. Preferred are the nitrogen atom leaving groups described in No. b/ri or the arylthio groups described in US Pat. Further, the pyrazolone coupler having a ballast group described in European Patent No. 73.4jA provides high color density.

As a pyrazoloazole coupler, US Patent No. 3.
36? , No. 17 is a dazole compound, preferably pyrazolo(j,/-cJ [/, λ, IAJ triazoles, ri-chi disclosure) described in U.S. Pat. 2 Hiro 220 (
Examples thereof include the pyrazolotetrazoles described in Section K 1 (/r≠month of the year) and the pyrazolopyrazoles described in Research Disclosure 2u230 (r≠month of the year). Imidazo(/,2-1)J pyrazoles described in European Patent No. 1/2, 7tA/ are preferred from the viewpoint of low yellow side absorption and light fastness of coloring dyes, and European Patent No. 1/2, rt, pyrazolo [/.

j-bJ(/, 2.Hiro) tri/-al is particularly preferred.

Examples of uncouplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, as disclosed in US Pat. ≠7 Hiroshi.

2′? No. 3, preferably the naphthol couplers described in U.S. Pat.

Typical examples include the oxygen atom separation type 2-equivalent 7 toll couplers described in /Hiro 6, 3 Ri Otsu, Ko λr, No. 233 and Ko No. 4, 200. It will be done. Further, specific examples of phenolic couplers are shown in U.S. Pat.
．． 367, Octopus No. 2, Octopus No. 2,10/171, Octopus No. 2,772,162, Octopus No. λ, tj, No. 222, etc. Against humidity and temperature? Difficult cyan couplers are preferably used in the present invention and include, for example, phenolic couplers having an alkyl group higher than ethyl group in the meta-position of the phenolic nucleus as described in U.S. Pat. No. 772.002. System uncoupler, US Patent No. 2
, No. 772, 112, No. J, 7! lr, No. 301, 1i44. /u4. JPJ No. ≠, 33≠, θ
// No. ≠, No. 327゜173, West German Patent Publication No. 3
, 32, 7 Kota issue special application Showa rr - ≠ 2, which was written in Koro issue 77, etc.! - Diacylamino-substituted phenolic couplers and U.S. Patent No. 3. ≠4L Otsu, Otsu λλ,
Hiroshi Dodai, 333. It has a phenylureido group at the 11th position and has an acylamino group at the 1st position, as described in Tatata issue, Hiromu Hiro, Hiroyo/, Jrj issue, and issue ≠, ≠, 27, '#7, etc. These include phenolic couplers.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate spreading property. Such dye-diffusive couplers are described in US Pat. /2, specific examples of magenta couplers are described in No. 670, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 370 and West German Application No. 3, 2344゜633. .

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A good example of a polymerized dye-forming coupler is US Patent No. J, IA! r/
, No. 120 Oyo and Same No. U, oro.

It is described in issue 2//. Examples of polymerized magenta couplers are described in British Patent No. 2,10λ,773 and US Pat. No. 44,347, λt2.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more different layers using the same compound. It can also be introduced into

The coupler used in the present invention can be introduced into the light-sensitive material by an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is /
After dissolving in either a high boiling point organic solvent of 7j0C or higher and a low boiling point so-called auxiliary solvent alone or in a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. . Examples of high boiling point organic solvents are described in US Pat. No. 2.3λ Co.,027 and others. Dispersion may be accompanied by phase inversion (or, if necessary, auxiliary solvents may be removed or reduced by distillation, noodle washing, ultrafiltration, etc.) before use for coating.

Specific examples of high-boiling organic solvents include phthalate esters (digtyl 7-talate, dicyclohexyl 7-pv-t,
di-λ-ethylhexyl phthanate, defluftanoate, etc.), esters of phosphoric or phosphonic acids! (triphenyl phosphate, tricresyl phosphate, λ-
Ethylhexyl diphenyl phosphate, triditalohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, trypto+diethyl phosphate, trichloropropyl phosphate, dicoethylhexyl phenyl phosphate, etc.), benzoic acid esters (to 2-ethyl xyl benzoate,
dodecyl benzoate, coethylhequinyl p-hydroquine benzoate, etc.), amides (diethyl dodecanamide, hetetradeneruvirolidone, etc.), alcohols or phenols (stearyl alcohol, U, tert-amylphenol, etc.) Such)
, aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributisate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-λ-butquine-j-tert-octylaniline, etc.), Examples include hydrocarbons (terafin, dodecylbenzene, diisopropylnaphthalene, etc.). In addition, as an auxiliary bath agent, the boiling point is about J o
0C or more, preferably jo0c or more and about /100c or less, organic G series etc. can be used, and typical examples include ethyl acetate,
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, λ-ethyne ethyl acetate,
Examples include dimethylformamide.

The process and effects of latex dispersion methods and examples of latex moldings for impregnation are disclosed in US Pat.

No. 363, West German Patent Application (OLS) No. 2. ! Hiroshi/.

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

Standard convenient values for color couplers range from 0.00 to 1 mole per mole of photosensitive silver halide, preferably yellow couplers with ij 0,0 /
fl or 0.5 mol, magenta coupler 0.00
3 to Oo, 3 moles, and 0.0 for cyan couplers
02 to 0.3 mol.

The light-sensitive material produced using the present invention can be used as a color antifogging agent or a color mixing inhibitor, such as hydroquinone derivatives, abanophenol derivatives, amine compounds, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, and black coloration. It may also contain couplers, sulfonamide phenol derivatives, and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydronones,
6-Hydroxychromans! -Hydroquine coumarans, spirochroman Lp -Alkoxy/phenols, bisphenols, all-centered hindered phenols, gallic acid derivatives, methane dioxybenzenes, aminophenols, dirt amines, and the phenolic properties of these compounds Typical examples include ether or ester derivatives in which the hydroxyl group is heptalylated or alkylated. Also, (bissalicylaldoximado) nickel complex and (bis-N,N-dialkyldithiocarbamide)
Metal complexes such as nickel complexes can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Patent No. ψ,26r,j23,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent deterioration of the agenta dye image, especially deterioration caused by light, spiroindanes described in JP-A-6L-4913J, VC-described in JP-A-6L-4913J, Talomanes substituted with non-diethers or monoethers give favorable results.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This ultraviolet absorbing 4J may be co-emulsified with a cyan coupler.

It is possible to apply the ultraviolet absorber in an amount sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is generally preferable to use /×10 mol/m −2×10 “mol/”s especially! ×70
Mol/m ~ノ,! It is set in the range of xl0-3 mol/m2.

In a normal color pH sensitive material layer structure, an ultraviolet absorber is contained in one layer on either side adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers, between the green-sensitive layer and the red-sensitive layer. When adding an ultraviolet absorber to the intermediate layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or radiation.

The photographic emulsion layer or other aqueous colloid layer of the light-sensitive material of the present invention may contain a brightening agent such as a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble ones may be used, and water-free brighteners may also be used in the form of dispersions.

As mentioned above, the present invention is applicable to multilayer, multicolor photographic materials having a small number of different spectral sensitivities on a support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has one green-sensitive emulsion layer and one blue-sensitive emulsion layer.

The order of these layers can be selected as desired, but in order to maximize the effects of the present invention, it is preferable to place the blue-sensitive emulsion layer as the uppermost layer, in which case the red-sensitive emulsion layer,
The order of the green-sensitive emulsion layers can be selected as desired. Further, each of the above-mentioned emulsion layers may be composed of λ or more emulsion layers having different sensitivities (or a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity).

In addition to the silver halide emulsion layer, the light-sensitive material according to the present invention is preferably provided with auxiliary layers such as a protective layer, an intermediate layer, a back layer, and a protective layer.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin conductors, graft polymers of gelatin and other Karasu molecules, proteins such as albumin and casein;
Cellulose derivatives such as hydroquine ethyl cellulose, carboxin methyl cellulose, cellulose sulfate esters, etc., sugar derivatives such as sodium alginate, starch-containing conductors;
Various types of synthetic hydrophilic polymers such as single or copolymers of polyvinyl alcohol, polyhinyl alcohol partial acetal, polyhevinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. material? Can be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, and Phot.

Enzyme-treated gelatin such as that described in Japan, yFcu &, page 30 (/riOtsu 6) may be used (also,
Hydrolyzed gelatin and enzymatically decomposed products can also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, chemicals or their precursors,
Development accelerators or precursors thereof, lubricants 41, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are Research Disclosure/71
．． (43 (/7g year/J month) Oyobido/17/A(/
It is written in 7 years//month).

(Example) Next, the present invention will be explained in more detail based on examples.

Implementation Iy11-1 Table I was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper having a layer structure shown in vc was prepared. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (a) /2, /9 and color image stabilizer (b)
) 4′, 4′, 9 with ethyl acetate 27 , 27+11 and solvent fc) 7 .

5'd was added and dissolved, and this solution was emulsified and dispersed in Q% gelatin water gi/rjd containing 10% sodium dodecylbenzenesulfonate lrd.

The emulsified dispersion and emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table I to prepare a seventh layer coating solution.

The coating liquids for the λth layer to the seventh layer were also prepared in the same manner as the first layer coating liquid. The gelatin hardening agent for each layer is l-on-3. J-dichloro-8-triazine sodium salt was used.

The emulsion used in the present invention was prepared as follows.

Add NaCl2'A to the 3-thigelatin water bath solution of rioocc.

2g and KBr/, /i were added and dissolved. This bath liquid is
ooc and 77% AgNO3 under strong stirring g2! , cc and a water bath solution containing ioog of KBr and 379 of Na in 1OOOCQ were added by a tag jet method. The amount of the halogenated alkaline water heart fluid added was adjusted so that the pAg at the beginning of t'j1 was maintained.

Subsequently, the above-mentioned aqueous solution of AgNO3 j64.1ACC and aqueous alkali halide solution were added by double jet method. At this time, the AgNO3 water bath solution was added every minute (CC)
Accelerate the addition so that m1n) becomes V-μ, ≠ 10, /3ft after t minutes from the start of addition 710, and adjust the alkali halide water bath solution to maintain the initial pAg. did.

After further removing soluble salts using a sedimentation method, gelatin was added to redisperse the mixture, and sodium lithiosulfate (t) per mole of silver halide was added to optimally chemically sensitize it at jOoC.

The emulsion thus obtained is referred to as Emulsion A. In emulsion A, 20% of the total projected area of the contained silver halide grains is occupied by tabular grains, and the average thickness of the tabular grains is o, i≠μ, and average as. The cut ratio was 7. In addition, the average particle size was measured using a Coulter Counter TA model manufactured by Coulter Electronics, and was found to be 0.
It was a 70μ door. Further, the content of AgBr was rr% by mole. Diameter Y of a circle having an area equal to the projected area when silver halide grains of emulsion A are dispersed on a plane
When d, the value obtained by dividing one standard deviation S of d by the average value d of d multiplied by ioo (h is called the coefficient of variation) is
/ It was Tati.

In the formulation of emulsion A, / row A g N O3 water @
Emulsion B, which has a profile substantially similar to that of Emulsion A except for a standard deviation of 13%, was created by reducing the rate of addition of 270 rogenated alkaline water and lowering the preparation temperature. I got it.

In the formulation of emulsion A, 3 N added to the thigelatin water bath solution.
By changing the aα amount and KBr amount appropriately, the alkali halide aqueous solution added to toooaa was mixed with KBr7/, ug and N.
Emulsion C was obtained in the same manner except that a+Jj was changed to an aqueous solution containing sg and pAg was lowered for control. The AgBr content of Emulsion C was 60 mol. Also,
Emulsion C had a coefficient of variation of silver halide grains of /tachi. The emulsion profile of Emulsion C other than these was substantially similar to Emulsion A.

In the formulation of emulsion A, before starting the addition of the AgNO3 aqueous solution and the alkali chloride solution, KT was added to the reaction vessel, and in the same way as emulsion B, the AgN
An emulsion with an AgI content of 3 and a tilt dynamic coefficient of 1 was obtained by reducing the addition rate of the O3 aqueous solution and the alkali chloride solution. The profile of the other emulsions was substantially similar to Emulsion A.

Next, a method for preparing a silver chlorobromide emulsion for comparison will be described.

2 jg of 3% gelatin water bath solution iCNaC of oocc was added and dissolved. This solution was kept at 700C, and under strong stirring, 10 cc of 77% AgNO3 aqueous solution was added.
% KBr and 5% NaCl was added by double jet method over 60 minutes.

Thereafter, chemical sensitization was optimally carried out in the same manner as in Emulsion A to obtain Emulsion E.

The shape of emulsion E is blocky, and the average grain size is 0.70.
μ door, A g B r content was rs morch. The coefficient of variation of silver halide grains in Emulsion E was /7.

In the formulation of Emulsion E, the AgNO3 aqueous solution and the alkali chloride solution were each divided into two molar ratios of /:λhiro. The AgNO3 aqueous solution and the alkali halide aqueous solution having the smaller molar number were added, and then the AgNO3 aqueous solution having the larger molar number and the aqueous alkali halide solution were added.

By appropriately changing the addition rate of these two /ξ-ts and the temperature of addition 1, an emulsion F having a coefficient of variation of ITS was obtained. Emulsion F had a substantially similar profile to Emulsion E except for the coefficient of variation.

In the formulation of emulsion E, the amounts of KBr and Naα in the aqueous alkali solution were changed appropriately to contain AgBr! 6
0 molti...variation coefficient of silver halide grains/tachi...
Silver halogenide emulsion G was prepared. The emulsion profile of Emulsion G other than these was substantially similar to Emulsion E.

By appropriately lowering the preparation temperature and pAg in the formulation of Emulsion A, Emulsion I was obtained by modifying Emulsion H. The average powder size of emulsion H is 0.1413 m, and the coefficient of variation is 1.
ra4 and what is the AgBr content? It was Omorchi. The average powder size of Emulsion I was O.Uλμ, the coefficient of variation was 72%, and the A g Br content was 70 mol. The other profiles of Emulsion H and Emulsion I were substantially similar to Emulsion A.

In the formulation of emulsion E, the preparation temperature is lowered and the
・KBr and NaQ in rogenated alkali solution? Emulsion J and Emulsion K were obtained by appropriately changing the amount of . The average grain size of Emulsion J was O0≠5μ, the coefficient of variation was /T, and the AgBr content was 10M. The average particle size of the emulsion was O1≠2μ, the coefficient of variation was /P%, and the AgBr content was 70 mol. The profiles of Emulsion J and Emulsion other than those described above were substantially similar to Emulsion E.

In the formulation of emulsion A, N added to 3% gelatin in water
The amount of aα and the amount of KBr were changed appropriately, and the amount of KBr was 3.0% in 10ooac of the halogenated alkali water heart fluid to be added. rp and N
aC1j! An emulsion was obtained in the same manner except that the aqueous solution was changed to an aqueous solution containing . The emulsion has an average thickness of 0476
μm, average aspect ratio is 4, AgBr content is 20
The coefficient of variation of the silver halide grains was 10%. The emulsion profile of the emulsion other than these was substantially similar to Emulsion A.

Emulsion M was also obtained in the same manner except that in the formulation of the emulsion, the amount of Naα and KBril added to the 3% gelatin aqueous solution were changed appropriately, and the pAg was appropriately increased and controlled. The AgBr content of emulsion M was tAO mol, and the emulsion profile other than this was substantially the same as emulsion M.

Emulsion ~ was obtained in the same manner except that the preparation temperature was appropriately lowered in the emulsion formulation. The average grain size to the emulsion is C
The emulsion profile other than this was substantially the same as that of the emulsion.

Emulsion O was obtained in the same manner as Emulsion M except that the preparation temperature was lowered appropriately. The average grain size of emulsion 0 is 0
．． 1413m, and the emulsion profile other than this was substantially the same as Emulsion M.

In the formulation of emulsion E, the amounts of KBril and Naα in the I/logenated alkaline water @ solution were changed appropriately to obtain emulsions P and Q with AgBr contents in the ratio of −0 molar and tI−Q molar. Emulsions P and Q were both cubic in shape, average grain size was 0.70 μ77 g, and the coefficient of variation of silver halide grains was /′?%.

Emulsion R was obtained in the same manner as Emulsion P except that the preparation temperature was lowered appropriately. The average grain size of emulsion R is O
1≠μm, and the emulsion profile other than this was substantially the same as Emulsion P.

In addition, when preparing an emulsion by adding a spectral sensitizing dye as described later, the amount of dye (7・OxlQ
Emulsion S, which was added at mOl/silver halide/mol, was also prepared.

In the preparation of emulsion A-8 above, AgN in the AgNO3 aqueous solution added together with the alkali chloride solution
2TrC1 is added to the nuclear alkali chloride aqueous solution so that the number of moles of O3 is /X/0-6 moles.
6 was contained.

Further, in the above emulsion preparation, spectral sensitization was carried out by adding the following spectral sensitizer at the end of chemical sensitization.

The numbers in parentheses under the structural formula of each spectral sensitizer are the amounts added for emulsions with bulk or cubic grain shapes.
When adding 270 to the tabular grains of the present invention, 1 times the amount (
For example, in the blue-sensitive emulsion layer /, lk x 10 mOl
/'' silver oxide/mol) (excluding the above-mentioned emulsion S).

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer (7.0×10 mol added per silver halide/mo+) Green-sensitive emulsion layer 5O3HN (C2)15) 3 (U per silver halide/mo+, oxio mollA added) 803 NH(C2Hs) 3 (Silver halide/7 per mo, OxlQ-5 moli 7L) Red-sensitive emulsion layer (Silver halide/per mo1, 0x10'mol added) The anti-irradiation dyes for each emulsion layer are as follows:
Department was used.

Green-sensitive emulsion layer: 5O3K SO3, red-sensitive emulsion layer: Cobbler, etc. The structural formulas of the compounds used in this example are as follows.

(at Yellow coupler C) i3 (b) Color image stabilizer (c) f8 medium ○H (e) Magenta coupler (fl Color image stabilizer (g) 2:/mixture of solvents (weight ratio) (h) Ultraviolet absorption Agent C4) 19 (t) CH2CH2COOC8H1□ /:! :3 mixture (molar ratio) (i) Color mixing inhibitor 0H U) Solvent (is o Cg Hl g O+3 P=0(k+
/:/ll alloy molar ratio of cyan coupler) (1) Color image stabilizer C4H9(t) R c4H9(t) /:3:j mixture (molar ratio) (m) Solvent The sample shown in the table/ Samples (b) to (e) with the profiles shown in Table 2 were prepared in the same manner using the same procedure except for the silver chlorobromide emulsion used.

Using a photosensitive layer (FWI (type, color temperature of light source 3200') K manufactured by Fuji Photo Film Co., Ltd.) for the above samples (A) to 4, samples for Sensitome IJ- were passed through blue, green, and red filters. Gives gradation exposure. The exposure at this time is O, S
The exposure time was 2 seconds and the exposure amount was 2 j OCM S.

Then, use color developing solutions (A) and (B) as shown below.
Experiments for treatments A and B were conducted using the following.

The processing consisted of the steps of color development, bleach-fixing, and washing with water, and the experiment was conducted with a development time of 2 minutes. The contents of treatments A and B represent the differences between the color developing solutions (A) and (B), and the other treatment contents are the same for both A and B.

(Processing process) (Temperature) (Time) Phenomenon 1
Solution Jr'C2.0 minutes Bleach-fix solution 3r'C1.0 minutes Water Washing 21r-3!0C3.0 minutes (Developer formulation) Color developer (A) Diethylenetriaminepentaacetic acid.! ~a 2.09 benzyl alcohol l! d Diethylene glycol lOp Na2SO32, Og KBr /, Op hydroxylamine sulfate 3.09≠-amino-
3-Methyl-h-ethyl-N-[β-(methanesulfonamido)ethyl)-p-phenydiathane sulfate r, ogNazCO
3 (/water salt) 30.0g fluorescent brightener (stilbene type) /, add 0g water to make the total amount
/ 000p (pH 10,2) Color developer (B) diethylenetriaminepentaacetic acid/jNa 2 , O
gNa2SO32,09 KBr 1. og hydroxy/ruamine sulfate 3.09≠-amino-3-methyl-hemony-dithylhe [β-(methanesulfonamido)ethyl J-p-fuunidiathane sulfate j, OgN a 2
C03 (/water salt) 3 o, og Fluorescent brightener (stilbene type) i, og water added to total amount / 000 g (pH/ 0, 2
) (Bleach-fix solution formulation) Common to processing A and B> Ammonium thiosulfate (JHiro wt%) 130ml Na2
SO3/! 9 NH4(Fe (III) (EDT A)J 5'IEDTA
--2Nau and water were added to make the total amount 1ooogo(p)4A, ri) The results obtained are shown in Table 3. The relative sensitivities in each treatment in Table 3 are relative values when the sensitivity in treatment A of each of the photosensitive layers of samples (a) to (4) is taken as 100. Is the sensitivity the concentration with o and r on the side of the minimum concentration? It is expressed as a relative value of the reciprocal of the exposure amount required to give

In addition, as a guideline for determining the degree of decrease in color density when processing B is performed, the density / when processing A is performed.

The color density when processing B was performed at the exposure amount giving j was taken. Therefore, it can be said that the closer the density is to /,j, the more efficient color development the photographic material exhibits.

Furthermore, the fog value when processing B is performed is shown together with the capri value when processing A is performed.

From Table 3, samples (a) using the emulsion of the present invention for BL ~
(・→, Example, (In the case of January, the benzyl acetate of treatment B
:ff-/l/fl showed good photographic performance similar to that of qA with benzyl alcohol, and it was shown that sufficiently high color density could be obtained even with short-time processing.

On the other hand, in the sample of the comparative example, it was shown that efficient color development (color development could not be achieved) was achieved with a short development time.

The samples of the present invention also showed lower fog without benzyl alcohol, indicating that the combination with color development without benzyl alcohol is more preferable.

Example-2 Samples (3) to (3) shown in Table 1 were prepared in the same manner as in Example-1.
) was prepared and the same test as in Example-1 was conducted.

In this example, in order to examine the effect of improving color reproducibility, the difference in sensitivity between the blue sensitive layer, the green sensitive layer, and the red sensitive layer when exposed through a blue filter was used as an evaluation measure of color reproducibility. It means that the larger the sensitivity difference, the better the color reproducibility.

The difference in sensitivity is calculated by correcting the sensitivity of each layer so that each sample reproduces gray when exposed to white light. It is shown as the value when

Show your results! Shown below.

From the table, it can be seen that the combination of the present invention provides lower capri and higher coloring density as in Example 1 even when used in each layer of B%G and R, and when used in all layers. I understand.

Furthermore, it is clear that when the tabular grains of the present invention are used, the color reproducibility is improved as evidenced by the sensitivity difference during blue filter exposure (in treated BvC). It can be seen that the example shows good color reproducibility. This effect was particularly remarkable for tabular grains with a high silver chloride content, and those with a blue-sensitive layer on top were shown to have very good color reproduction. A sample using a cubic high-silver chloride silver chlorobromide emulsion showed good color reproduction, but the Capri value was too large (unsuitable for practical use).

(Effects of the present invention) By carrying out the present invention, it is possible to significantly reduce the pollution load by substantially reducing benzyl alcohol (D--), reduce the liquid preparation work, and reduce the amount of cyan dye remaining in the leuco form. In addition, it is possible to quickly process large quantities of color prints with improved color reproducibility, dramatically improving productivity.Furthermore, according to the present invention, benzyl alcohol A color current f that does not substantially contain
Even if a short-time treatment is performed with liquid I, a good color image with little decrease in color density (and low capri) can be obtained.

Patent applicant Fuji Photo Film Co., Ltd. Mr. Commissioner of the Japan Patent Office
February 20, 1931 Patent application (1) 3. Relationship with the case of the person making the amendment Person who applied for the patent Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact Address: 106 Higashi (Nishi 1 Cup, Miyako Minato Ward) (Ii 2-1” r 126 each No. 30 4,
We will submit an engraving of the date of the amendment order: Voluntary Issue 5, the subject of the amendment, the specification 6, and the details of the amendment (no changes have been made to the contents).

Claims (1)

[Claims] at least 50% of the total projected area of silver chlorobromide and/or silver bromide grains substantially free of silver iodide on the reflective support;
A photographic light-sensitive material coated with at least one silver halide photographic emulsion layer containing tabular grains having an average aspect ratio of 5 or more is subjected to imagewise exposure and then treated with a color developer substantially free of benzyl alcohol. A color image forming method characterized by developing within 2 minutes and 30 seconds.