JPH01221746A - Processing of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prompt bleaching effect of a color-developed silver halide color photographic sensitive material and to shorten a processing time by executing color development of the material having a silver halide emulsion layer comprising monodisperse silver halide particles having no chemically sensitized twin face on a base in the presence of a sensitizing dye, then treating with a specified treating soln. as a bleaching agent. CONSTITUTION:An emulsion comprising monodisperse particles having high quantum efficiency but having no internal defect, i.e., twin face, in the inside of the particles, is contained in a silver halide color photographic sensitive material. Further, the emulsion is chemically sensitized in the presence of a spectral sensitizing dye. Moreover, at least one kind of ferric complex salt of compds. selected from (A-1) ethylenediamine tetraacetic acid, (A-2) diethylenetriamine pentaacetic acid, (A-3) cyclohexanediamine tetraacetic acid, and (A-4) 1,2-propylenediamine tetraacetic acid, is incorporated into a treating soln. having bleaching effect as a bleaching agent together with ferric complex salt of 1,3-diaminopropane tetraacetic acid in <=3:1 proportion by mole of the former to the latter, when the material is treated after color development with a treating soln. having bleaching effect. Thus, sufficient bleaching is attained in a short time.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, particularly those that have excellent color reproducibility and sharpness, high sensitivity, and wide exposure latitude. The present invention relates to a silver halide color photographic light-sensitive material obtained. The present invention also relates to an improved development processing method capable of accelerating the bleaching action, shortening the processing time, and performing sufficient bleaching action to form color photographic images of good quality.

(Prior art) Research on sensitization technology regarding silver halide grains includes, for example, research that theoretically calculated the quantum efficiency of silver halide and considered the influence of particle size distribution, which was conducted in 1980 on the progress of photography.
Proceedings of the 2018 Tokyo Symposium “Interaxins”
Between Light and Materials for Photographic Applications, page 91. This research suggests that creating a monodisperse emulsion is effective in improving quantum efficiency, that is, it is possible to increase sensitivity.

In addition, in particles having twin planes inside the particles, the twin planes themselves act as internal defects (because of this, it is expected that they often become an inefficient factor in the photosensing process).

Therefore, particles without such internal defects and without twin planes can be preferably used as highly sensitive particles.

Furthermore, by chemically ripening the grains in the presence of a dye, it is possible to obtain a color-sensitized emulsion with high sensitivity and good storage stability by strengthening the adsorption of the dye and reducing the inherent desensitization caused by color sensitization. For example, it is possible to
, No. 941.

By the way, when the emulsion prepared by the above-mentioned dye addition method is used in a color photographic light-sensitive material, after color development, it is treated with a bleach solution or a bleach-fix solution using widely used ethylenediaminetetraacetate iron (1) tt salt. However, the efficiency of desilvering decreases, probably due to the strong adsorption of dyes, making it difficult to shorten the processing time despite the high sensitivity and excellent preservability. The situation was such that it was difficult to form accurate color photographic images.

(Problems to be Solved by the Invention) An object of the present invention is to provide a color photosensitive material with high sensitivity and excellent storage stability and durability, which can be improved by sufficiently desilvering even in a short period of time after imagewise exposure. An object of the present invention is to provide an improved processing method capable of forming color photographic images.

(Means for Achieving the Object) The color photographic light-sensitive material of the present invention contains an emulsion consisting of grains that are monodisperse and have high quantum efficiency and do not have internal defects called twin planes within the grains. Since the emulsion has a step of chemical sensitization in the presence of a spectral sensitizing dye, the color photographic material of the present invention has high sensitivity and good storage stability. Furthermore, when this color photographic light-sensitive material is processed with a processing liquid having bleaching ability after color development processing, the processing liquid having bleaching ability is a ferric compound selected from the following compound group (A) as a bleaching agent. When processed by a processing method containing at least one type of complex salt and a ferric complex salt of 1,3-diaminopropanetetraacetic acid in a molar ratio of the former to the latter of 3 or less, it exhibits characteristics of high sensitivity and good storage stability. The present inventors have found that good derailment efficiency is exhibited while maintaining the derailment.

Compound Group (A) A-1 Ethylenediaminetetraacetic acid A-2 Diethylenetriaminepentaacetic acid A-3 Cyclohexanediaminetetraacetic acid A-41,2-Propylenediaminetetraacetic acid The process of chemical sensitization of the emulsion of the present invention involves the use of spectral sensitizing dyes. It is essential to include a step carried out in the presence of. However, the case where the chemical sensitization process is completed by adding a spectral sensitizing dye is also included in the above process. Does this type of dye addition method control crystal growth during particle formation? It is used for the purpose of making a sensitizing dye act as a control agent for photonucleation during IJP+ or chemical sensitization. Further, such a dye addition method results in adsorption of the dye onto the particles at a high temperature of 50° C. or higher, and is used for the purpose of promoting enhancement of adsorption.

In the present invention, the end of afterripening refers to the stage at which the progress of chemical sensitization has stopped.

The spectral sensitization described in the present invention can be carried out at any stage of emulsion preparation known to be useful, as long as it is before the completion of chemical ripening.

Spectral sensitization can be performed simultaneously with chemical sensitization, as taught in U.S. Pat. It is also possible to start spectral sensitization before the end of . It is also possible, as taught in US Pat. No. 4,225,666, to have a portion of the spectral sensitizing dye present in the step before chemical sensitization is complete, and the remainder to be introduced after chemical sensitization.

In other words, the spectral sensitizing dye may be added at any step before grain formation, during grain formation, during physical ripening, or before the water washing step, or before chemical sensitization, during chemical sensitization, or after the end of chemical sensitization. It may be added at any time immediately before.

The species of spectral sensitizing dye used in the present invention is not particularly limited.

Dyes for use in the present invention include polymethine dyes including cyanine, merocyanine, complex cyanine and complex merocyanine (i.e. tritetra-1 and polynuclear cyanine and merocyanine), oxole, hemioxonolstyryl, merostyryl and streptocyanine. is included.

Cyanine spectral sensitizing dyes include quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz(
e) Indolium, oxacillium, oxazolinium, thiazolium, thiazolinium, selenazolium, selenacylinium, imidazolium, imidazolinium,
Benzoxacillinium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, thiazolinium, dihydronaphthothiazolium, sodium and imidazopyrazinium quaternary It contains two basic heterocyclic nuclei connected by a methine bond, as derived from the class salt.

Merocyanine spectral sensitizing dyes include barbituric acid, 2-
Thiobarbic acid, rhodanine, hydantoin, 2-
Thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3-dione, cyclohexane-1,3-dione, 1,3-dioxane-4,6- cyanine dye types with acidic nuclei such as those derived from diones, pyrazoline-3°5-dione, pentane-2,4-dione, alkylsulfonylacetonitrile, malononitrile, isoquinolin-4-one and chroman-2,4-dione. Various supersensitization techniques can be used for color sensitization in the present invention, including those in which a basic heterocyclic nucleus is bonded via a methine bond. Examples of useful dye combinations, including supersensitizing dye combinations, include U.S. Pat.
No. 672.898. An example of a supersensitizing combination consisting of a spectral sensitizing dye and a non-light absorbing additive is the use of thiocyanate in the process of spectral sensitization, as shown in U.S. Pat. No. 2,221.805; U.S. Pat. No. 2,933,390 and using sootriazinylaminostilbene as shown in U.S. Pat. No. 2,933,390.
7,089, mercapto-substituted heterocyclic compounds as shown in U.S. Patent No. 3,457,078, British Patent No. 1.413, Iodide can be used as shown in No. 826.

In addition, the method for adding the sensitizing dye to the photographic emulsion is as follows:
Various methods proposed in the past can be applied. For example, as described in U.S. Pat. No. 3,469.987, a sensitizing dye is dissolved in a volatile organic solvent and the solution is dispersed in a hydrophilic colloid. Alternatively, the sensitizing dyes of the present invention may be dissolved individually in the same or different solvents and these solutions may be mixed before being added to the emulsion. , can be added separately.

In the present invention, when adding the sensitizing dye to the silver halide emulsion, examples of the dye solvent include methyl alcohol,
Water-miscible organic solvents such as ethyl alcohol and acetone are preferably used.

In the present invention, when the sensitizing dye is added to the silver halide emulsion, the amount added is 1 x 10 per mole of silver halide.
-S mole to 2.5X10-' mole is preferred, and more preferably 1.0X10-' mole to 1°0XIO-' mole.

The sensitizing dye can also be used in combination with other sensitizing dyes or supersensitizers.

In the present invention, particles without twin planes include regular particles widely used in the industry, such as cubic, octahedral, dodecahedral, and tetradecahedral particles, and JP-A-62 -123446, 46hedral grains described in JP-A No. 62-123447, or mirror index particles such as (310) planes as described in European Patent No. 213963A. Examples include particles consisting of higher-order planes with a sum of indexes exceeding 3. Further, two or more of these monodisperse regular particles can be used in combination. It can also be used in combination with particles having twin planes. But in this case,
It is preferable that 50% or more of the amount of gold and silver in the emulsion is the monodispersed regular grains.

In the present invention, monodisperse particles are defined as having a coefficient of variation of 0.25 or less given by S/r (S is the standard deviation regarding the particle size, T is the average particle size) when evaluating the equivalent volume sphere diameter. Refers to something that is. Regarding monodispersity in the present invention, the emulsion has a coefficient of variation of preferably 0.22 or less, more preferably 0.18 or less.

The present invention relates to a silver halide color photographic material comprising at least one silver halide emulsion layer on a support. In particular, when carrying out the present invention, the effect is remarkable in color-sensitized high-sensitivity silver halide color photographic light-sensitive materials, especially color reversal light-sensitive materials for shadows and color negative light-sensitive materials for photography, which use high-silver emulsions. It is.

In particular, when a light-sensitive material in which the emulsion of the present invention is used in a high-sensitivity layer with large grain size is processed with the processing solution of the present invention, the effect is remarkable. Further, the definition of a high silver content light-sensitive material using the above-mentioned high silver content emulsion is one having a silver content of 4 g/- or more.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The silver halide is silver iodobromide, silver bromide, or silver chlorobromide containing up to 30 mol % of silver iodide.

The grain size of the silver halide may be fine grains of 0.1 micron or less, or large grains with a projected area diameter of up to 10 microns.

The method of reacting the soluble root salt with the soluble halide salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. A method in which zero particles are formed in an excess of silver ions (so-called back mixing method) ) can also be used. As one type of simultaneous mixing method, a method in which the number of layers (g) in the liquid phase in which silver halide is produced is kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and pH during grain formation. For more information, see Photographic Science, & Engineering.
5ciens and engineering
) No. 6@, pp. 159-165 (1962); Journal of Photographic Science
al of Photographic 5ci
ence), vol. 12, pp. 242-251 (1964
), U.S. Pat. No. 3,655.394 and British Patent No. 1,413.748.

The crystal structure of these emulsion grains may be --like, the inside and outside may have different halogen compositions, or they may have a layered structure.
No. 46, U.S. Patent No. 3,505.068, U.S. Patent No. 4,44
No. 4,877 and Japanese Patent Application No. 58-248469.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, silver halides, rhodan silver,
It may be bonded with a compound other than silver halide, such as lead oxide.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As a further variant, ripening agents can also be introduced at the halide salt and silver salt addition stage.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. Special Publication No. 5B-1410, Moisar et al., Journal of Photographic Science, Vol. 25, 1977.19
As described on page 27, silver halide emulsions can be sensitized by internal reduction of grains during the precipitation formation process.

The location of chemical sensitization varies depending on the composition, structure, and shape of the emulsion grains, as well as the intended use of the emulsion.When chemical sensitization nuclei are embedded inside zero grains, when they are embedded at a shallow position from the grain surface, Alternatively, chemical sensitizing nuclei may be created on the surface. Although the effects of the present invention are also effective, particularly preferred is the case where chemically sensitized nuclei are created near the surface. In other words, surface latent image type emulsions are more effective than internal latent image type emulsions.

Chemical sensitization is described in James (T, HlJames), The Photographic Process, 4th edition, published by Macmillan, 1977 (7, 1, JBme's, T
the theory of the photog
rapic Process, 4thed,
Macmillan, 1977), pages 67-76, and also Research Disclosure 120S, 1
April 974, 12008; Research Disclosure, Volume 34, June 1975, 13452, U.S. Patent Nos. 2,642,361, 3,297,446, 3,772.031, 3, No. 857,711, 3
．． 901. 714, 4,266.018, and 3°904.415, as well as British Patent Nos. 1 and 3.
pAg5-10, pAg5-10 as described in No. 15°755
It can be carried out using sulfur, selenium, chilli, gold, platinum, palladium, iridium or a combination of these sensitizers at H5-8 and a temperature of 30-80°C.

Chemical sensitization is optimally carried out in the presence of gold compounds and thiocyanate compounds, and in the presence of sulfur-containing compounds as described in U.S. Pat. Chemical sensitization can also be carried out in the presence of a chemical sensitization aid, carried out in the presence of a sulfur-containing compound such as a compound or hypo, a thiourea compound, or a rhodanine compound. Chemical sensitization aids used include azaindene,
Compounds known to suppress fog and increase sensitivity in the process of chemical sensitization are used, such as azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are U.S. Pat.
No. 14, No. 3,554,757, JP-A-58-126
No. 526 and the aforementioned Duffin, "Photographic Emulsion Chemistry", 13
It is described on pages 8-143. In addition to or in place of chemical sensitization, reduction sensitization can be performed, for example with hydrogen, as described in U.S. Pat. US Patent No. 2
．． stannous chloride, as described in No. 518,698, No. 2,743.182 and No. 2,743.183;
Reduction sensitization can be performed using reducing agents such as thiourea dioxide, polyamines, and the like, or by low pAg (eg, less than 5) and/or high pH (eg, greater than 8) treatments. Color sensitization can also be improved by chemical sensitization methods described in US Pat. No. 3,917.485 and US Pat. No. 3,966.476.

Furthermore, the chemical sensitization method described in Japanese Patent Application No. 59-213957 is particularly effective when combined with the emulsion of the present invention.

The various additives described above are used in the photosensitive material related to the present technology, but various other additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure+-Ekes 17643 (December 1978).
and Ite1118716 (November 1979)
The relevant sections are summarized in the table below.

Additive type RD17643 1701B7
161 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers, Pages 23-24 Page 648 Right column - Super sensitizers Page 649 Right column 4 Brighteners
Page 24 5 Antifogging agent Pages 24-25 Page 649 Right column and Stabilizer 6 Light absorber, filter 25-26 True 649 Right column ~ Ilter dye 650 Left column.

Ultraviolet absorber 7X? (:/Inhibitor 25 page right 1rjI650
Page left to right column 8 Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant page 27 650 Right column 12 Coating aid, table Pages 26-27 Same as above Surface activator 13 Pre-flux prevention agent Page 27 Same as above Various color couplers can be used in the present invention A specific example of this can be found in the aforementioned Research Disclosure (RD
) Nal 7643, ■-C to G.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, 4.022,620, 4.3
No. 26.024, No. 4.401゜752, Special Publication No. 5
B-10739, British Patent No. 1.425.020,
No. 1,476.760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0.619, No. 4.351°897, European Patent No. 73.636, US Patent No. 3.061.432, No. 3. 725. No. 067, Research Disclosure 11h24220 (June 1984), JP-A-6
No. 0-33552, Research Disclosure Na
24230 (June 1984), JP-A-60-4365
No. 9, U.S. Patent No. 4,500.630, U.S. Patent No. 4.54
Particularly preferred are those described in No. 0.654.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4.146.396, No. 4.228.23
No. 3, No. 4. 296. No. 200, No. 2.369
, No. 929, No. 28801.171, No. 2.77
2.162, 2,895.826, 3,7
72. G.

No. 2, No. 3.758.308, No. 4,334.0
No. 11, No. 4.327.173, West German Patent Publication Tube 3
．． 329,729, European Patent No. 121.365A,
U.S. Patent No. 3. 446. No. 622, No. 4,333
, No. 999, No. 4,451.559, No. 4.42
7.767, European Patent No. 161,626A, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure Magnet 17643.
- Section G, U.S. Patent No. 4.163゜670, Special Publication No. 1983
-39413, U.S. Patent No. 4.00'4,929,
Same No. 4. 138. No. 258, British Patent No. 1,146
, No. 368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． 570, EP 96,570 and DE 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820, U.S. Pat. No. 4.080.211, U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
No. 2.131.188, JP 58-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include U.S. Patent No. 4. 130. Competitive couplers described in U.S. Pat. No. 427, etc., U.S. Pat.
Long equivalent coupler described in JP-A-60-18595
0, DIR redox compound or DIR coupler releasing coupler or DI described in JP-A-62-24252 etc.
R coupler releasing coupler or redox, a coupler releasing a dye that after separation described in EP 173,302A, R,D, 11449, 24241
Examples include bleach accelerator-releasing couplers described in JP-A No. 61-201247 and the like, and ligand-releasing couplers described in U.S. Pat. No. 4,553,477 and the like.

The bleaching agent of the present invention comprises at least one ferric complex salt of a compound selected from the compound (A) group and a ferric complex salt of 1゜3-diaminopropanetetraacetic acid, the molar ratio of the former to the latter being 3 or less. Used together at a ratio of (including 0). The preferable molar ratio is 1.8 to 0.5. If the molar ratio exceeds 3, the bleaching strength will decrease and desilvering will be poor. Furthermore, if the ratio of ferric salt of 1,3-diaminopropanetetraacetic acid becomes extremely high, slight bleaching fog may occur.

The amount of the bleaching agent of the present invention added is 0.05 mol to 1 mol, preferably 0.1 mol to 0.5 mol, per 11 baths having bleaching ability.

In addition to the above-mentioned aminopolycarboxylic acid iron (III) complex, an aminopolycarboxylic acid salt can be added to the treatment liquid having bleaching ability of the present invention. In particular, it is preferable to add a compound of compound group (A).

Hereinafter, the treatment bath having bleaching ability of the present invention will be explained.

In the present invention, immediately after color development, processing is carried out in a processing bath having bleaching ability.

A processing bath having bleaching ability generally refers to a bleaching solution and a bleach-fixing solution, but in the present invention, a bleaching solution is preferred because it has an excellent bleaching blade, and the desilvering process of the present invention includes, for example, the following steps. However, it is not limited to these.

■ Bleach-fixing ■ Bleach-bleach-fixing ■ Bleach-fixing ■ Bleach-fixing-bleach-fixing ■ Bleaching-Water-washing and fixing Particularly, steps (1) and (2) are preferred in order to exhibit the effects of the present invention.

The preferred amount added is 0.0001 mol to 0.0001 mol. 1 mole/
It is more preferably 0.003 mol to 0.05 mol/l.

Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred because they have excellent solubility and bleaching properties.

Further, the bleach solution or bleach-fix solution containing the above-mentioned ferric ion complex may contain a metal ion complex salt other than iron, such as cobalt or copper.

Various bleach accelerators can be added to the bath having bleaching ability of the present invention.

Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, German Patent No. 1,290.
, 812, British Patent No. 1 138.842, JP-A-53-95630, and Research Disclosure No. 17129 (July 1978 issue). Compounds, thiazolidine derivatives described in JP-A No. 50-140129, thiourea derivatives described in U.S. Pat. No. 3,706.561, iodides described in JP-A-58-16235, German patents Polyethylene oxides described in specification No. 2,748.430, Japanese Patent Publication No. 1974-
Polyamine compounds described in Japanese Patent No. 8836 can be used. Particularly preferably British Patent No. 1,138,
Mercapto compounds such as those described in '842 are preferred.

As bleach accelerators, compounds represented by general formulas (IA) to (VIA) are preferred.

General formula (IA) RIA-8-MIA In the formula, MIA represents a hydrogen atom, an alkali metal atom, or ammonium. RlA represents an alkyl group, an alkylene group, an aryl group, or a heterocyclic residue. The alkyl group preferably has 1 to 5 carbon atoms, most preferably 1 to 3 carbon atoms. The alkylene group preferably has 2 to 5 carbon atoms. Examples of the aryl group include phenyl and naphthyl groups, with phenyl being particularly preferred. As the heterocyclic residue, nitrogen-containing 6-membered rings such as pyridine and triazine, and nitrogen-containing 5-membered rings such as azole, pyrazole, triazole, and thiadiazole are preferred, but among these, two or more of the ring-forming atoms are nitrogen. Particularly preferred is an atom. RIA may be further substituted with a substituent. Examples of substituents include alkyl groups, alkylene groups, alkoxy groups, aryl groups, carboxy groups, sulfo groups, amino groups, alkylamino groups, dialkylamino groups, hydroxy groups, carbamoyl groups, sulfamoyl groups, sulfonamide groups, etc. Can be done.

- Preferred among formulas (IA) are - formulas (IA)
-1) to (IA-4).

-Formula (IA-1) 〒′” RsA-N-(CH*)kA-SH(ZlA)IA(R
'IIA In the formula, RlA, RtA, and R4A may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted lower alkyl group (preferably having 1 to 5 carbon atoms, and particularly preferably a methyl group, an ethyl group, or a propyl group). ) or an acyl group (preferably a carbon number of 3 to 3, such as an acetyl group or a propionyl group), and kA is an integer from 1 to 3. Zl
A is anion (chloride ion, bromide ion, nitrate ion,
sulfate ion, p-toluenesulfonate, oxalate, etc.). k and A represent 0 or I, and iA represents 0 or l.

R" and R" may be linked to each other to form a ring. R.I.
A, R'' and R4A are preferably a hydrogen atom or a substituted or unsubstituted lower alkyl group.

As the substituent for R", R", R", a hydroxy group, a carboxy group, a sulfo group, an amino group, etc. are preferable.

General formula (IA-2) General formula (IA-4) In the crystal formula, RSA represents a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), an amino group, a substituted or unsubstituted lower alkyl group (preferably 1 to 5 carbon atoms, particularly preferably methyl, ethyl, and propyl groups), amino groups having alkyl groups (methylamino, ethylamino,
Represents a substituted or unsubstituted alkylthio group (dimethylamino group, diethylamino group, etc.).

Examples of the substituent that R'' has here include a hydroxy group, a carboxy group, a sulfo group, an amino group, and an amino group having an alkyl group.

General formula (nA) RIA-85-RlA In the formula, RlA is the same as RlA of general formula (IA),
R" is synonymous with RIA. RIA and RIA may be the same or different.

Among general formulas (tlA), preferred ones are general formulas (n
A-1).

General formula (IIA-1) In the formula, R'1^, RlA, R-^ are RlA, RlA, R
It is synonymous with 4A. hA, kA and 21A are expressed by the general formula (IA
-1) (7) hA and kA are the same as ZlA. iB
is o.

! or 2.

General formula (n[) In the formula, R16A1RIIA may be the same or different, and each represents a hydrogen atom, an alkyl group that may have a substituent (preferably a lower alkyl group, such as a methyl group, an ethyl group, a propyl group) ), a phenyl group which may have a substituent,
or a heterocyclic residue that may have a substituent (more specifically, a heterocyclic group containing at least one heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc., such as a pyridine ring,
thiophene ring, thiazolidine ring, benzoxazole ring, benzotriazole ring, thiazole ring, imidazole ring, etc.). R'' represents a hydrogen atom or a lower alkyl group which may have a substituent (for example, a methyl group, an ethyl group, etc., preferably having 1 to 3 carbon atoms).

Here, the substituents from RIILIA to R1'' include a hydroxy group, a carboxy group, a sulfo group, an amino group, a lower alkyl group, and the like.

R''A represents a hydrogen atom, an alkyl group, or a carboxy group.

General formula (fVA) In the formula, RI", R15A, and R'.^ may be the same or different, and each hydrogen atom or lower alkyl group (e.g., methyl group, ethyl group, etc.) preferably has 1 to 3 carbon atoms. kB represents an integer from 1 to 5.

XIA represents an amino group, a sulfo group, a hydroxy group, a carboxy group, or a hydrogen atom which may have a substituent. The substituent is a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, hydroxyalkyl group, alkoxyalkyl group, carboxyalkyl group, etc.), and two alkyl groups may form a ring.

R1", R"A% R'" may be linked to each other to form a ring. R""'-R"' is particularly a hydrogen atom,
A methyl group or an ethyl group is preferred, and xIA is preferably an amino group or a dialkylamino group.

- Formula (V A) (H) pa Here, A" is an n-valent aliphatic linking group, aromatic linking group, or heterocyclic linking group, (when n = 1, AIA is a simple aliphatic group, an aromatic linking group, The aliphatic connector group represented by AIA (representing a group group or a heterocyclic group) has 3 carbon atoms.
~12 alkylene groups such as trimethylene, hexamethylene, cyclohexylene, etc. may be mentioned.

Examples of the aromatic linking group include arylene groups having 6 to 18 carbon atoms (eg, phenylene, naphthylene, etc.).

Examples of the heterocyclic linking group include a heterocyclic group consisting of one or more heteroatoms (e.g., oxygen atom, sulfur atom, nitrogen atom) (e.g., thiophene, furantriazine, pyridine,
piperidine, etc.).

Here, the number of aliphatic linking groups, aromatic linking groups, and heterocyclic linking groups is usually one, but two or more may be linked, and the linkage may be direct or with a divalent linking group (for example, - 〇－
1-s-1Rt.^-3Ot-N-1 -1-〇〇- or a linking group formed from these linking groups, and RlA represents a lower alkyl group).

Further, the aliphatic linking group, aromatic linking group, and heterocyclic linking group may have a substituent.

Examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, a hydroxy group, a carboxy group, a sulfo group, a sulfonamide Y group, and a sulfamoyl group.

X mushroom ＾ stands for 10-1-S-1RIIA.
N- is a lower alkyl group (e.g. methyl group, ethyl group, etc.)
), R1'l^ RIIA represents a substituted or unsubstituted lower alkyl group (e.g., methyl group, ethyl group, propyl group, isopropyl group, pentyl group, etc.),
Examples of the substituent include a hydroxy group, a lower alkoxy group (for example, a methoxy group, a methoxyethoxy group, a hydroxynidoxy group, etc.), an amino group (for example, an unsubstituted amino group,
Dimethylamino group, N-hydroxyethyl-N-, methylamino group, etc.) are preferable; here, when there are two or more substituents, they may be the same or different.

R191 represents a lower alkylene group having 1 to 5 carbon atoms (methylene, ethylene, trimethylene, methylmethylene, etc.), and zt' represents an anion (halide ion (chloride ion, bromide ion, etc.), nitrate ion, sulfate ion, p-)
luensulfonate, oxalate, etc.).

Also, RI? ^ and R1^ are connected via a carbon atom or a heteroatom (e.g. oxygen atom, nitrogen atom, sulfur atom), and 5
or 6ji members (for example, a pyrrolidine ring, a piperidine ring, a morpholine ring, a triazine ring, an imidazolidine ring, etc.).

RI'& (or RImA) and A are connected via a carbon atom or a hetero atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom), and form a 5- or 6-membered heterocycle (e.g., a hydroxyquinoline ring, a hydroxyindole ring). , isoindoline ring, etc.).

Furthermore, R1(or RIIA) and R19^ are connected via a carbon atom or a heteroatom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom), and form a 5- or 6-membered heterocycle (e.g., a piperidine ring). , pyrrolidine ring, morpholine ring, etc.).

jlA is 0 or 1, mA is O or 1, nA is 112 or 3, pA is 0 or 11 and QA is 0.1.2 or 3
represents.

General formula (VIA) R: Tomi＾

Ml^ is hydrogen atom, alkali metal atom, ammonium s
In R1t^, R11A represents a hydrogen atom or a lower alkyl group (having 1 to 5 carbon atoms and which may have a substituent).

Specific examples of compounds of general formulas (IA) to (VIA) are shown below.

(IA)-+11 (IA)-+21 (IA)-(31 (IA)-(41 (IA)-(5) C.I.

C■.

(IA)-(6) (IA) -(10) -N -N (1^)-(+';) 1xA) -(+7) N N(1A)''
(Ig) N-8CH""N"'8H CIA)-(2o) (I[A) -(1n(IIA) -(:+ (IIA) -(31 (■^)-(season(...A) ) -(53 (11A) -(6) (to II)-(7) (IIA)-(3) (■^)-(%l) (■A) -(to) (HA)-ell ([ IA) -(2) ([[IA) -(t+ (II[A)-121 (IA) -(3) (I[[A) -(4) (IA)-(5) (ILA)-( 6) '(1vA) - (1 (WA) - (2) (ffA) - (3) (ffA) - (4) (to W) - (5) (mA) - (6) (ffA) - (7) (to Tv) -(8) (iVA) -(9) (WA) -(10) (TvA) -(11) (WA)-(/) to H,N(CH2CH20H) 2 (V^ )-(J) 由(VAI-(J) (FAI-('') (rA) (t) UH, N(CH, CH, OH).

(V^1-(Hun) (Ma ^) - (f) +.

ffA) @0? ) Import (7s) -(rs(V^)-(/J) (74%-(/g) (Ma)-(/73 什＾)-(/4) (V^)-(l foot (r^)-(/I) CH,N(C)(,CH,OCH,Cl-1,OH)
R(ma^l-(/F) υh (ma^)-(J e) (ma^J-(J/J (WA)-(J J) y^)-(ko3) (V^)- (KOIA) (V^)-(Stiffness (vA)-<2t) (VIA)-(11 H5 (VIA)-+s+) (VIA)-+31 (VIA)-+41 (VIA)-(61 The above bleaching Among the accelerators, particularly preferred compounds are IA-2,!
A-5, IA-13, IA-14, IA-15, IA-
16, IA-19, [IA-1, IIA-IL VA
-1, VIA-1, and VIA-2. The amount of bleaching accelerator added is 0.01g to 20g per 11 of the bleaching agent.
g, preferably 0.1 g to Log.

In addition to the bleaching agent and the above-mentioned compounds, the bleaching solution constituting the present invention includes bromides such as potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide or chlorides such as potassium chloride, sodium chloride, ammonium chloride can be included.

The concentration of the rehalogenating agent is from 0.1 to 5 mol, preferably from 0.5 to 3 mol, per 1 β of bleaching solution. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate,
pHff of citric acid, sodium citrate, tartaric acid, etc.
Additives known to be commonly used in bleaching solutions, such as one or more types of inorganic acids, organic acids, and salts thereof, each having a single buffering capacity can be added.

The pH of the bleaching bath of the present invention is generally 6 to 1, preferably 5.8 to 1.5, most preferably 5.8 to 1.5.
It is 3-2. In a preferred pH range, there is little bleaching fog and excellent desilvering performance.

The replenishment amount of the bath having bleaching ability of the present invention is 50 mjt to 2000 m1 per 1 d of light-sensitive material, preferably 100 mj!
~1000mj! It is.

In the present invention, after treatment with a bath having bleaching ability, treatment is generally performed with a bath having fixing ability.

However, this does not apply when the bath having bleaching ability is a bleach-fixing solution.

The bath having fixing ability in the present invention refers to a bleach-fixing bath and a fixing bath.

Fixing agents for baths having these fixing abilities include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate; thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate; urea,
Thioether etc. can be used. The amount of these fixing agents is 0.3 mol to 3 mol, preferably 0.
5 moles P-2 moles.

The fixing bath contains sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite adducts of hydroxylamine, hydrazine, aldehyde compounds, such as acetaldehyde sodium bisulfite. be able to. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, but in particular, as preservatives, it is possible to contain
It is preferable to use the sulfinic acid compounds described in No. 283,831.

The replenishment amount of the bath having fixing ability is preferably 300 mj to 3 Q OQml per 1 d of photosensitive material, more preferably 300 m1 to 1000 mm! It is.

Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the bath having fixing ability of the present invention for the purpose of stabilizing the solution.

The shorter the total time of the desilvering step of the present invention, the more remarkable the effects of the present invention can be obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes.

Furthermore, the treatment temperature is 25°C to 50°C, preferably 35°C to 4°C.
The temperature is 5°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62-18346.
No. 0, No. 62-183461, the method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, and the method of colliding a jet of a processing liquid on the emulsion surface of a photosensitive material, as described in JP-A No. 62-183-1.
No. 83461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. method, and a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used in the present invention is JP-A-60-191
257, No. 191258, and No. 191259. As described in JP-A-60-191257, such a conveying means is used to transfer from the front bath to the post bath. It is possible to significantly reduce the amount of processing liquid carried into the process, and it is highly effective in preventing the performance price of the processing liquid from increasing.This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl-N −(β
-(methanesulfonamide)ethyltwoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N -ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Furthermore, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. Preferably about 0.1 g to about 20 g,
More preferred is a concentration of about 0.5 g to about 10 g.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

The preferable addition amount is 0.5g-1 per 11 color developer.
0 g, more preferably 1 g to 5 g.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Hydroxamic acids described in No. 9, hydrazines and hydrazides described in No. 61-170756, and hydrazides described in No. 61-188
Phenols described in No. 742 and No. 61-203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or No. 61-18
Various I! described in No. 0616! It is preferable to add
In addition, in combination with the above compounds, patent application No. 147823/1986
No. 61-166674, No. 61-165621, No. 61-164515, No. 61-170789,
and monoamines described in No. 61-168159, etc.
No. 61-1'73595, No. 61-164515,
Diamines described in No. 61-186560, etc., No. 61
-165621 and the polyamines described in No. 61-169789, the polyamines described in No. 61-188619, the nitroxy radicals described in No. 61-197760, No. 61-186561, and No. 61-19741.
It is preferable to use alcohols described in No. 9, oximes described in No. 61-198987, and tertiary amines described in No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
The aromatic polyhydroxy compound described in No. 746.544 may be included if necessary, and addition of an aromatic polyhydroxy compound is particularly preferred.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, O-
Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2
-sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0. 1 mole/
It is preferably 1 or more, especially 0.1 mol/1 to 0
．． Particularly preferred is 4 mol/l.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-1-rimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, transcyclohexanecyaminetetraacetic acid, 1.2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-)licarboxylic acid,
1-hydroxyethylidene-1,1-diphosphonic acid, N
, N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used in combination as necessary.

The amount of these chelating agents added may be sufficient as long as the amount is sufficient to sequester metal ions in the color developer. For example, 11
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain Hensyl alcohol from the viewpoint of pollution, formulation properties, and prevention of color staining. Here, "substantially" refers to '1 ml or less, preferably not at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 3B-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3.
813,247, etc., p-phinidine diamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50=137726, JP-B-Sho. 44- 30074, JP-A-56-156826 and JP-A-52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2,
No. 494,903, No. 3,128゜182, No. 4,2
30. '796, No. 3,253.919, Special Publication No. 4
No. 1-11431, U.S. Patent No. 2,482,546,
Amine compounds described in 2,596,926 and 3,582.346, etc., Japanese Patent Publication No. 37-16088,
No. 42-25201, U.S. Patent No. 3,128.183
Polyalkylene oxides disclosed in Japanese Patent Publications No. 11431/1983, 23883/1983, and US Pat. Can be added.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-Chia.

Representative examples include nitrogen-containing heterocyclic compounds such as zolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. Among the fluorescent brightening agents, 4゜4'-diamino-2,2'-disulfostilbene compounds are preferred. . The amount added is θ~5g/j! Preferably 0.1g to 4g/
j! It is.

Further, various surfactants such as alkylsulfonic acid, ary-phosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The amount of replenishment is preferably small, but is 100 to 150 Qml, preferably 100 to 800 ml, per 1nf of photosensitive material. More preferably 100
mj! ~400m1.

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

The processing method of the present invention can also be used for color reversal processing. In the present invention, the black and white developer used at this time is commonly known as the black and white first developer used for the reversal processing of color photographic light-sensitive materials, or Those used for processing black and white angry light materials can be used. In addition, various well-known additives that are generally added to black and white developers can be included.

Typical additives include l-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. I can give it to you.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above.

Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. A simple treatment method can also be used.

The rinsing water used in the rinsing step can contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Disinfectants and anti-fungal agents (for example, isothiazolones, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, surfactants that prevent drying load and unevenness, and the like can be used. Or L, E
.

West, “Water Quality Cr1t
eria”, Phot, Sci, andEng,, vo
l, 9. Na6, Pages 344-359 (1
965) and the like can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that can stabilize a dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing an aldehyde (for example, formalin), etc. can be used. The stabilizing liquid may optionally contain ammonium compounds, metal compounds such as Bi and A1, optical brighteners, chelating agents (for example, 1-hydroxyethylidene-1,1-diphosphone fa), bactericides, anti-fungal agents, A hardening agent, a surfactant, etc. can be used.

Further, the water washing step and the stabilization step are preferably carried out by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

The filtrate used in these washing steps or stabilization steps includes tap water, as well as Ca
, Mg? It is preferable to use water that has been deionized to have an f1 degree of 5 mg/l or less, water that has been sterilized with halogen, an ultraviolet germicidal lamp, or the like.

In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution due to evaporation may occur, especially when the processing amount is small or the opening area of the processing solution is large. becomes. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step is allowed to flow into a bath having a fixing ability, which is a pre-bath.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 Silver nitrate, KBr and! in gelatin aqueous solution! A silver halide emulsion was prepared by adding the solution using the Chondrald double jet method so that the silver potential was constant. The particle formation time potential is -40 mV to form octahedral particles.
and +10 mV to form dodecahedral particles. The temperature was kept at 75° C. and the pH at 5.5 during precipitation formation.

After the emulsion underwent the usual desalting process, gelatin and water were added for dispersion.

In this way, the average spherical equivalent diameter (hereinafter referred to as average particle diameter) 1
．． An octahedral monodisperse silver iodobromide emulsion and a tetradecahedral monodisperse silver iodobromide emulsion having a 1 μm silver iodide content of 10 mol % and a coefficient of variation regarding grain size of 0.17 were prepared.

The emulsions thus prepared were named Emulsion 1 (octahedral) and Emulsion 2 (decahedral).

An emulsion was prepared by adding silver nitrate, KBr, and Kl to an aqueous gelatin solution by quantitative addition in the same manner as in Emulsion 1.2 so that the iodine content was 10 mol %.

The same was true for emulsions 1 and 2, but during precipitation, the emulsion temperature was maintained at 75° C., the pH was maintained at 5.5, and sufficient stirring was performed. In this way, the average sphere equivalent diameter is 1. A polydisperse silver iodobromide emulsion having an octahedral structure with a coefficient of variation regarding grain size of 0.28 at 1 μm was prepared, and this was designated as Emulsion 3.

Color sensitization B was applied to these three emulsions in the multilayer examples described later.
Color sensitization was carried out using dyes described as ,G,R. At this time, chemical sensitization was also optimally performed using a gold/sulfur sensitizer, but the following classifications were made depending on the timing of chemical sensitization and color sensitization.

i) A sensitization method in which a dye is added before the start of chemical sensitization is called sensitization method α.
shall be.

ii) A sensitization method in which chemical sensitization is completed by addition of a dye is referred to as sensitization method β.

iii) When the chemical sensitization is completely completed, the temperature of the emulsion is raised to 40°C.
Sensitization method T is a sensitization method in which a dye is added after the temperature is lowered to .degree.

Based on these classifications, the color sensitized emulsions shown in the table below were prepared and classified according to differences in emulsion type, amount of dye (amount of dye contained), and sensitization method.

/ Table 1 Using these emulsions, the following color multilayer tofu samples 101.
102.103.104.105.106 were created.

The table below shows the samples and the emulsions used.

Table 2 (Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/l, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

1st layer; antihalation layer black colloidal silver...silver 0.18 gelatin
... 0.40 second layer; middle layer 2.5-di-t-pentadecylhydroquinone ... 0.18EX-1.
... 0.07 EX-3-... 0.02 EX-12... 0.002 U-1... 0.06 0-2... 0.08U-3
... 0.1O HBS-1 ... 0.10 8BS-2 ... 0.02 Gelatin ... 1.04 Third layer (first red-sensing breast layer) Monodisperse silver iodobromide emulsion (Silver iodide 6 mol% average grain size 0.
Coefficient of variation for 6 μm 1 particle size 0.1... Silver 0.55 Sensitizing dye I... 6.9X10-' Sensitizing dye ■... 1.8X10-' Sensitizing dye ■
... 3. lX10-'sensitizing dye■
... 4.0X10-SEX-2... 0.35
0 HBS-1... 0.005 EX-10... 0.020 Gelatin... 1.20 Fourth layer (second red-glare emulsion layer) Tabular silver iodobromide emulsion (silver iodide 10 mol) %, average particle size 0.7μ, average aspect ratio 5.5, average thickness 0.2μ
)...Silver 1.0 Sensitizing dye ■...5. lX10-'sensitizing dye■...1.4X10-'sensitizing dye■
...2.3XIO-'sensitizing dye■
・・・3.0X10-SEX-2・ ・ ・ 0
．． 400 EX-3・ ・ ・ 0.050 EX-10・ ・ ・ 0.015 Gelatin ・・・ 1.30 Fifth layer (third red-sensitive emulsion layer) Any of the color sensitized species R specified in Table 1 That emulsion.

...Silver 1.60 (color sensitization R) EX-3... 0.240 EX-4-... 0.120 HBS-1... 0.22 HBS-2... 0.10 Gelatin ... 1.63 6th layer (intermediate layer) EX-5... 0.040 HBS-1... 0.020 Gelatin ... 0.80 7th layer (first green emulsion layer) Flat plate silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 6.0, average thickness 0.15) ...1!0.40 Sensitizing dye ■ ...3.0XlO-' Sensitizing dye ■ ...1.0X10-' Sensitizing dye ■
...3.8XIQ-'EX-6...0
．． 260 EX-1... 0.021 EX-1... 0.030 EX-8... 0.025 HBS-1... 0.100 HBS-4... 0.010 Gelatin... 0.75 8th layer (second green emulsion layer) Monodispersed silver iodobromide (silver iodide 9 mol%, average grain size 0.75)
7μ Coefficient of variation regarding particle size 0.18) ・ ・ 1 0, 80 Sensitizing dye V ・・2. lX10-'sensitizing dye■...7.0X10-'sensitizing dye■
...2.6X10-'EX-6...0
．． 180 EX-8... 0.010 EX-1... 0.008 EX-7... 0.012 HBS-1... 0.160 HBS-4... o, ooa Gelatin... l, 10 9th layer (third green emulsion layer) Any emulsion specified by color sensitizing type G in Table 1... Silver 1.2 (color sensitizing G) EX-6... 0 .065 EX-11... 0.030 EX-1... 0.025 HB S -1... 0.25 HBS-2... 0. lO Gelatin... 1.74 1st O layer (
Yellow filter N) 1 yellow colloid ・ ・ ・ilo, 05
EX-5... 0.08 HBS-3... 0.03 Gelatin... 0.95 11th layer (
1st blue emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 5.7, average thickness 0.15μ
)...Daughter 0.24 Sensitizing dye ■...3.5X10-'EX-
9・ ・ ・ 0.85 EX-8・ ・ ・ 0.12 HBS-1・ ・ ・ 0.28 Gelatin ・・・ 1.28 12th layer (
2nd blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (21110 mol% iodide, average grain size 0.8μ, coefficient of variation regarding grain size 0°...
i艮0, 45 Sensitizing dye■...2. lX10-'EX-
9... 0.20 EX-10... 0.015 HBS-1... 0.03 Gelatin... 0.46 13th layer (
3rd blue-sensitive emulsion layer) Any emulsion specified by color enhancing type B in Table 1
... 0.77 (color sensitization B) (sensitizing dye ■ ...2.2XIO-'EX
-9・ ・ ・ 0.20 HBS-1・ ・ ・ 0.07 Gelatin ... 0.69 14th layer (
1st protective layer) Silver iodobromide emulsion (silver iodide 1 mol%, average grain size 0.07μ) 0, 5 U-4... 0.11 U-5... 0. 17 HBS-1... 0.90 Gelatin... 1.00 15th layer (
2nd protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) ---0,543-1・
... 0.15 3-2 ... 0.05 Gelatin ... 0.72 In addition to the above-mentioned components, gelatin hardening agent H-1 and a surfactant were added to each layer.

EX-2 0H EX-3 0■ EX-4 H EX-5 EX-4 EX-7 EX-1 EX-5' C00Ct□)1.
, (nlX-10 R CH.

S-/S-CoHBS-/) Recresyl 7onu7ate HBS-co Dibutyl 7-thaletate HBS-J and 2(λ-ethylexyl)phthalate HBS-ψ H-/ Sensitizing dye! C2m(s ■ (shih2), jU3NM After the imagewise exposure of the samples prepared as described above, each sample was continuously processed (running test) until twice the tank capacity of color developer was replenished in the following processing step. I did it.

However, the composition of the bleaching solution was changed as shown in Table 1, and the test was conducted for each of them.

The automatic developing machine used was of the belt conveyance type described in JP-A No. 60-191257, and each processing bath was
The jet stirring method described in No. 183460 was used.

The processing steps are shown below.

Color development 3 minutes 15 seconds 38℃ 38-1 Bleaching 1 minute 38℃ 4m
g Fixing 1 minute 38℃ 3
0-1 Stable 1 20 seconds 38℃ - Stable 220 seconds 38℃ - Stable 3 20 seconds 38℃ 35g+#*Dry
1 minute 15 seconds 50-70°C - *The stabilizing liquid was a 3-tank countercurrent system of stable 3 - stable 2 - stable 1.

The composition of each treatment liquid used is shown below.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0
Potassium bromide 1.3 0.9
Potassium iodide 1.2mg
-Hydroxylamine sulfate 2.6 2.8
Add 4-[N-ethyl-N-β-4,75,3hydroxyethylamino]-2-methylaniline sulfate solution 1. (H! 1.
01p H10,0010,05 (Bleach solution) Mother liquor Replenisher solution 1.3 to diaminopropane tetraacetic acid ta 4. Og
5.0g ammonium bromide 100.
0g 160.0g ammonium nitrate
30.0g 50.0g Ammonia water (27%)
20.0 m123.0 ml! Acetic acid (
98%) 9. Or1115. O
Add ml water 1.011.01
pH See Table 1 HC1 (Fixer) Mother liquor Replenisher 1-Hydroxyethylidene-1,1-diphosphonic acid 5.0g 6.0g
Sodium sulfite 7.0g 8.0
gSodium bisulfite 5.0g 5.
5g Ammonium 1000sulfate 170.0ml!
200.0 ml water solution (70%) Add water 1. Qll, 0I2pH
6,76,6 (Stable solution) Mother liquor, replenisher common formalin (37%) 1.2 mj
! 5-chloro2-methyl-4- 6.0ff1g
Isothiazolin-3-one 2-methyl-4-isothiazo 3. Offig phosphorus-3-one surfactant 0.4 [C, mountain+ -0+ CHxCHzO+rWH] ethylene glycol 1.0 Add water
i, o j! 1) H5,0-7,0 After exposing the sample to 20 CMS, it was treated with each running equilibrium solution, and the amount of residual silver was determined by fluorescent X-ray method.

◎: O~4.0μg/d ○: 4.1~? , O, crg/aj△:
7.1-10.0 μg/csJx: to, t-15.
0 μg/d xx: 15.1 μg/- or more As shown in Table 4, monodispersed emulsions without twin planes, in which dyes were present during chemical sensitization, were treated with the bleaching solution of the present invention. It can be seen that it shows good desilvering properties.

Similar results were also confirmed for the bleaching solution of the present invention containing A-2, A-3, and A-4 in the compound group (A).

Said coating sample 101.102.103.104.105
．． No. 106 was exposed to light for sensitometry, and the following development treatment was performed. The concentration of the treated sample was measured using red, green, and blue filters. Further, after the sample was placed under forced deterioration conditions of high temperature and high humidity (45°C, 80% for 72 hours), a similar sensitometric test was conducted. The photographic performance results obtained are shown in Table 4.

The development process used here was carried out at 38°C under the following conditions.

1. Color development...2 minutes 45 seconds 2. Bleaching...6 minutes 30 seconds 3. Wash with water...3 minutes 15 seconds 4. Arrival: 6 minutes 30 seconds 5. Wash with water...3 minutes 15 seconds 6. Stability...3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide
1.4g hydroxylamine sulfate 2.4g 4-(N-ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate 4.5g Add water 11 Bleach solution Bleach solution A or D Fix solution Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium neosulfate 70%) 175.0mff1 Sodium bisulfite 4.6g Add water
11 Add 8.0 ml of stabilized formalin water and calculate the fresh sensitivity of sample 3 for blue, green, and red when A is used as the bleaching solution. It is shown in Table 4 as 100.

As is clear from Table 5, the color light-sensitive materials using the emulsions of the present invention exhibit high sensitivity and good storage stability even after being subjected to the processing of the present invention.

Further, when similar experiments were conducted with bleaching solutions B, C, E, F, G, and Hll, the same results as with solution D were obtained.

Example 2 A color multilayer photosensitive material was prepared on an undercoated cellulose triacetate film support, consisting of each layer having the composition shown below.

Emulsions 1, 2, and 3 prepared in Example 1 were used to prepare samples for the present invention and comparative examples. Similar to Table 2 of Example 1, Table 1 shows the relationship between the coated samples and the emulsions used.

In this example, since the dye type used for spectral sensitization of the emulsion is different from Example 1, the classification symbols are used as color sensitization B', G',
Regarding the timing of 0-spectral sensitization and chemical sensitization described in the composition of the multilayer below as R', α, as described in Example 1,
Classified by β and T.

Samples 201 to 206 prepared as described above were subjected to desilvering characteristics and fresh and forced deterioration sensitometry in the same manner as in Example 1. As in Example 1, the effects of the present invention were confirmed. It was confirmed that it was clear.
1 (Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/m unit, and for silver halide, it indicates the coating amount in terms of silver. However, for sensitizing dyes, the coating amount is expressed in g / m unit. The amount of coating per mole of halogenated w&1 is shown in molar units.

1st layer (anti-halation N) black colloid lil 0. 2 gelatin 1. 0 Ultraviolet concentrator UV-10,05 Same UV-20,1 Same UV-30,1 Dispersion oil 0IL-10,02 2nd layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ) Silver 0 .15 Gelatin 1. 0 Third layer (first red-sensitive emulsion layer) Monodispersed emulsion (silver iodide 6 mol%, average grain size 0.4 μm, coefficient of variation 15%) Silver 1.42 Gelatin 0.9 Sensitizing dye A
2.0X10-' sensitizing dye B
1.0X10-'sensitizing dye C0,3X1
0-' Cp-b 0. 35Cp-
co, 052 Cp-a o, 047D-1
0,023 D-20,035 HBS-10,10 HBS-20,10 4th layer (middle layer) Gelatin 0.8cp-b
o, 10HBS-10,05 5th layer (second red-sensitive emulsion layer) Monodisperse emulsion (silver iodide 6 mol%, average grain size 0.5 μm,
Coefficient of variation 15%) Silver 1.38 Gelatin 1.0 Sensitizing dye A
1.5X10-' sensitizing dye B
2.0X10-' sensitizing dye CO, 5xl
O-' Cp-b O,150Cp-
d o, 027D-10,0
05 D-20,010 HBS~1 0.0508BS-
20,060 Sixth layer (third red-sensitive emulsion layer) Any emulsion specified by R' in Table 1 2
, 08 (color sensitization R') gelatin 1.5Cp-aO,
060 Cp-cO, 024 Cp-d 0.038D-1
0,006 HBS-10,12 7th layer (middle layer) Gelatin 1. 0Cpd-A
O,05HBS-20,05 8th layer (first green-sensitive layer) Monodisperse silver iodobromide emulsion (silver iodide 3 mol%, average grain size 0.4 μm, coefficient of variation 19%) Dispersed silver iodobromide emulsion (6 mol% silver iodide, average grain size 0.7 μm, coefficient of variation 18%) Silver 1.12 Gelatin 1. 0 sensitizing dye D
lXl0-'sensitizing dye E
4X10-'sensitizing dye F
1xlO-'cp-h
o, 20Cp-f 0.61
cp-go, 084Cp-k
0.035Cp-10,03
6 D-30,041 D-40,018 HBS-10,25 HBS-20,45 9th layer (second green emulsion layer) Any emulsion silver specified by G' in Table 1 2.0
7 Gelatin 1. 5 (color sensitization G
') cp-r o, 007Cp-
h O,012Cp-g
O,009HBS-20,08
8 10th layer (middle layer) Yellow colloid! IO,06 Gelatin 1. 2Cpd-A
O,3HBS-I
Q, 3 11th layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.4 μm, coefficient of variation 20%) Silver 0.31 Monodisperse iodobromide emulsion Silver emulsion (silver iodide 5 mol%, average grain size 0.9 μm, coefficient of variation 17%) tio, 38 gelatin 2.0 sensitizing dye G
lXl0-'sensitizing dye HlXl
0-' Cp-io, 63 Cp-30,57 D-10,020 D-40,015 HBS-10,05 12th N (second blue emulsion layer) Any one specified by B' in Table 1 emulsion i 0
, 77 Gelatin 0.5 (color sensitization B'
) Cp-40,10 Cp-jo, 10D-40
,005 HBS-20,10 13th layer (middle layer) Gelatin 0. 5Cp-mO
, l UV-10, l UV-20, t UV-30, I HBS-I Q, 05HBS-
20,05 14th layer (protective layer) Monodisperse silver iodobromide emulsion (silver iodide 4 mol%, average grain size 0.0
5μ, coefficient of variation lθ%) 0, 1 Gelatin 1.5 polymethylmetharylate particles (average 1.5μ) 0.1 3-1 0. 23-2
0. 2. Other surfactants -1 and gelatin hardening agent H-1 were added.

Same F (CHz)asOJa -I Same G Same H 0H 1L-1 p-a H p-b H p-c p-d p-r p-g Cp-h CI' J Ca1
l, (n) ■ Cp-k Cp-II Cp -m BS-I B5-2 -1 ■ UV-1 Same as above UV-2 0 ■ UV-3 C,H.

Compound CpdA H H CHz = CH-5ow-CHz l' C1h = Cl-3 (h-CH2 Patent applicant Fuji Photo Film Co., Ltd. Procedural amendment (
Many illusions

Claims (1)

[Scope of Claims] A color photosensitive material having on a support at least one silver halide emulsion layer consisting of monodisperse silver halide grains having no twin planes that have been chemically sensitized in the presence of a sensitizing dye. After development, at least one ferric complex salt of a compound selected from the following compound group (A) as a bleaching agent and 1,3-
1. A method for processing a silver halide color photographic light-sensitive material, which comprises processing a silver halide color photographic light-sensitive material with a processing solution having a bleaching ability and containing a diaminopropanetetraacetic acid ferric complex salt in a molar ratio of the former to the latter at a molar ratio of 3 or less. Compound Group (A) A-1 Ethylenediaminetetraacetic acid A-2 Diethylenetriaminepentaacetic acid A-3 Cyclohexanediaminetetraacetic acid A-41,2-Propylenediaminetetraacetic acid