JPH04101136A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure high sensitivity, to reduce magenta stain and to improve incubation resistance and the shelf stability of a latent image by incorporating a silver halide emulsion chemically sensitized in the presence of a sensitizing dye added by >=1mmol per 1mol silver halide and using a specified bleaching soln. CONSTITUTION:This color photographic sensitive material has at least one photosensitive silver halide emulsion layer and the surfaces of the silver halide particles in the silver halide emulsion have been chemically sensitized in the presence of at least one kind of sensitizing dye added by >=1mmol per 1mol silver halide. A bleaching soln. used contains >=0.2mol/l iron (III) complex salt of aminopolycarboxylic acid having >=150mV oxidation-reduction potential as a bleaching agent. The sensitizing dye is added during the formation of the particles, between the end of the formation of the particles and desalting, between desalting and the beginning of post-aging, immediately before the beginning of post-aging or during post-aging. High sensitivity is ensured, magenta stain can be reduced and incubation resistance and the shelf stability of a latent image can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic materials (hereinafter referred to as color photographic materials).

More specifically, the present invention relates to a method for processing a color photosensitive material that has high sensitivity, improved magentastin, and excellent incubation resistance and latent image storage stability.

(Prior Art) In recent years, color photosensitive materials have become increasingly sensitive, and technological development for this purpose has been actively carried out.

As one of them, for example, Japanese Patent Application Laid-Open No. 55-26589
No. 61-103149 or No. 61133941 describes a technique of chemical sensitization in the presence of a sensitizing dye. As a result, the dye adsorption power is strengthened and the inherent desensitization caused by color sensitization is reduced, so that a highly sensitive color light-sensitive material can be obtained.

However, this technique had the drawback of producing magentastin after processing.

(Problems to be Solved by the Invention) A first object of the present invention is to provide a color photosensitive material that has high sensitivity and has less magentastin after processing. A second object of the present invention is to provide a desilvered color photographic material which further has excellent incubation resistance and latent image storage stability.

(Means for Solving the Problems) The above object is to provide a method for processing an imagewise exposed silver halide color photographic light-sensitive material with a bleaching solution after color development. contains an emulsion chemically sensitized in the presence of 1 mmol or more of a sensitizing dye per 1 mole of silver halide, and the bleaching solution contains iron aminopolycarboxylate (III) having a redox potential of 150 mV or more as a bleaching agent. ) Complex salt 0. 2 mol/l
This has been achieved by a method for processing a silver halide color photographic material, which is characterized by comprising the above.

This will be explained in detail below.

The color light-sensitive material of the present invention has at least one photosensitive silver halide emulsion layer, and chemical sensitization of the surfaces of halogen grains of the silver halide emulsion is carried out by using at least one sensitizing dye or one mole of silver halide. The process is carried out under conditions where 1 mmol or more of the compound is present. This chemical sensitization is performed by Siems (
T. H. James), The Theory of the...
Photographic Process, 4th Edition, Macmillan Publishing, 1977 (T, H, James, (Th
e Theory of thePhotograph
ic Process, 4th ed, Ma
cmillan.

1977) 6, p. 76, or using activated seratin as described in Research Disclosure, Vol. 120, April 1974, 12008:
Research Disclosure - Volume 34, June 1975,
13452. U.S. Patent No. 2,642,361, 3,
No. 297,446, No. 3,772,031, No. 3.
857. No. 711, No. 3,901,714, No. 4,
pAg 5-10, pH 5-8 and temperature 30-80° C.
The sensitizers may be sensitized using sulfur, selenium, chilli, gold, platinum, palladium, iridium, rhodium, or a combination of these sensitizers. Chemical sensitization is optimally
In the presence of a gold compound and a thiocyanate compound in the coexistence of at least one sensitizing dye and as described in U.S. Pat. 85
7. No. 711, No. 4,266.018 and No. 4,0
It is carried out in the presence of a sulfur-containing compound such as a sulfur-containing compound or a hypo, a thiourea-based compound, a rhodanine-based compound, etc., as described in No. 54-457. Chemical sensitization can also be carried out in the presence of other chemical sensitizing aids in addition to at least one sensitizing dye. The chemical sensitizing aid used is a compound known to suppress fog and increase sensitivity during the chemical sensitization process, such as asaindene, asapyridazine, asapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. No. 2,131,038, U.S. Pat.
No. 526 and the aforementioned Duffin, “Photographic Emulsion Chemistry,” 138
It is described on pages 143 to 143. In addition to chemical sensitization as described above, U.S. Pat.
Reduction sensitization can be performed using, for example, hydrogen, as described in U.S. Pat. No. 84,249, and U.S. Pat. 51
8. No. 698, No. 2,743,182 and No. 2,7
43°183 using stannous chloride, thiourea dioxide, polyamines and such reducing agents, or low p, Ag (e.g. less than 5) and/or high p
Reduction sensitization can be achieved by treatment with H (e.g., 8+). Also, U.S. Patent Nos. 3,917.485 and 3,917.485
, 966.476 can also be applied.

Furthermore, the sensitization method using an oxidizing agent described in JP-A-61-3134 and JP-A-61-3136 can also be applied.

The timing for adding the sensitizing dye may be during grain formation, after grain formation until desalination, from desalination until the start of post-ripening, immediately before the start of post-ripening, or during post-ripening. If it is added during grain formation, it is preferably added after 85% of the total silver nitrate has been added. When added during after-heating, it is preferable to add it before 50% of the total after-heating time.

The most preferable method is to add it between desalting and the start of post-ripening.

In the present invention, at least one light-sensitive silver halide emulsion is chemically sensitized in the presence of at least one or more sensitizing dyes.

Examples of sensitizing dyes that can be applied to the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex meronoanine dyes, holopholar dianine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. I can do it.

Useful sensitizing dyes for use in the present invention include, for example, U.S. Pat.
, No. 522,052, 3. 619. No. 197, No. 3,713.828, No. 3,615゜643, No. 3
, No. 615,632, No. 3,617.293, No. 3,
No. 628,964, No. 3゜703.377, No. 3,6
No. 66.480, No. 3.667.960, No. 3,67
No. 9,428, No. 3,672,897, No. 3,769
, No. 026, No. 3,556,800, No. 3,615,
No. 613, No. 3,615,638, No. 3,615゜6
No. 35, No. 3,705,809, No. 3,632.34
No. 9, No. 3,677.765, No. 3゜770.449
No. 3,770,440, No. 3,769,025, No. 3,745,014, No. 3,713,828,
No. 3,567.458, No. 3,625,698, No. 2. 526. No. 632, No. 2,503,776,
JP-A-4876525, Belgian Patent No. 691.80
It is stated in issue 7 etc.

The amount of the sensitizing dye added is 0.1 mmol or more per mol of silver halide, preferably 0.1 mmol or more. 1 mmol or more4
Less than mmol, more preferably 0.2 mmol or more1. It is 5 mmol or less.

In the present invention, it is particularly preferable to use the cyanine dyes shown below.

A cyanine dye suitable for use in the present invention is a compound represented by the following general formula (1).

General formula (I) R,R.

In the formula, 2. ．． 2. are thiazole nucleus, thiazoline nucleus, Hen's thiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus, oxaprine nucleus, naphthoxazole nucleus, imidazole nucleus, benzimidazole nucleus,
Represents the atomic group necessary to form an imidacilline nucleus, a selenazole nucleus, a selenazoline nucleus, a henzoselenazole nucleus, or a naphthoselenazole nucleus.

R,, R, represents an alkyl group or a substituted alkyl group.

However, at least one of R, and R2 shall have a sulfo group or a carboxy group.

L- and R2 represent a substituted or unsubstituted methine group.

n represents an integer from 0 to 2.

2. A substituent may be introduced into the nucleus formed by 22. Examples of the substituent include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aralkyl group, and a halogen atom.

R1 and R2 may be the same or different.

The alkyl group for R,, R2 is preferably one having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, heptyl, and the like. Examples of the substituent of the substituted alkyl group include carboxyne group, sulfo group, anano group, halogen atom (e.g. fluorine, chlorine, bromine), hydroxy group, alkoxycarbonyl group (having 8 or less carbon atoms, e.g. methoxycarbonyl, ethoxycarbonyl,
(pencil-oquine carbonyl), alkoxy groups (having 7 or less carbon atoms, such as methoxy, ethoxy, propoquine,
butquin, hensyloxy), aralkyl groups (e.g. fenoquine, ph-liluoquine), aceroxy groups (up to 3 carbon atoms, e.g. acetyloxy, propionyloxy), acyl groups (up to 8 carbon atoms, e.g. acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (e.g. carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarhamoyl), sulfamoyl groups (e.g. sulfamoyl,
N,N-trimethylsulfamoyl, morpholinosulfonyl), aryl groups (eg phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl). The number of carbon atoms in the substituted alkyl group is preferably 6 or less.

L As the substituted methine group, lower alkyl group (e.g. methyl, ethyl, propyl) Fe Nyl group, Examples include benzyl group.

Specific examples of sensitizing dyes effective in the present invention, including the above-mentioned cyanine dyes, are shown below.

(CH2)3 (CH2).

SO+ Na (CH2).

(CHz)+ So, K SO3HNEt3 So, K (CH,).

(CH2)t O3Na ■=3 ■ HCH3 HCH3 o3K O3 O3K SO3HNEt3 CH.

C2H.

(CH2).

S 03 Na ■ SO8 o3K (CH2)3 (CH2)3 03Na O3 2H5 (CH2)3 S03H-N(C2H6)3 O3 ■ ■ ■ (CH2)1 2Hs O3 S　Os　H-N(C2H6)3 SO; SO3NHEt3 2H5 03K SOL 2Hs C2H.

C, H5 (CH2), 5o3 C2H.

■-24 C2H5 C2H.

S○3K CH, C0OH 2H5 (CH2).

2H5 (CH2)3So.

r 2H5 ■-27 ■ ■ ■ 2 Hi ■ ■ ■ ■ ■ C,H.

The color light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of the emulsion layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. and the photosensitive layer is a unit photosensitive layer sensitive to any of blue light, green light, and red light,
In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in the following order from the support: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A No. 571
No. 12751, No. 62-200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL), or BH/BL/GL/GH/RH/RL, or B H/B L/GH/GL/RL /RH, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is arranged, and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is 0. Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing 1 to 30 mol% silver iodide. Particularly preferred is about 2 mol % to about 2 mol %.
Silver iodobromide or silver iodochlorobromide containing up to 5 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) N [L17643
(December 1978), pp. 22-23, “1. Emulsion preparation and
dtypes)” and same No. 18716 (19
November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Beaumontel (P, Glafkid
es.

Chemic et Ph1sique Photo
graphique, Paul Montel, 1
967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin.

Photographic Emulsion Che
Mistry (Focal Press.

1966)), "Manufacture and coating of photographic emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikm)
anet al,, Making and Co
ating Photographic Emulsi
on, Focal Press, 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
engineering), 1st
4, pp. 248-257 (1970); U.S. Patent No. 4
, 434°226, 4,414.310, 4,
No. 433.048, No. 4,439,520, No. 4゜4
No. 14.306, No. 4,459,353, Special Publication No. 1983
38692, Japanese Patent Application Laid-Open No. 62-209445, British Patent No. 2,112,157, and other publications disclose its manufacturing method and techniques for use.

In the present invention, the following monodisperse hexagonal tabular grains can be used.

The emulsion is a silver halide emulsion consisting of a dispersion medium and silver halide grains, in which 70% or more of the total projected area of the silver halide grains has a maximum area of 70% or more relative to the length of the side having the minimum length. It is a hexagonal shape in which the ratio of the lengths of its sides is 2 or less, and is occupied by tabular silver halide having two parallel surfaces as outer surfaces, and further, the hexagonal tabular halogen Coefficient of variation of grain size distribution of silver oxide grains [value obtained by dividing the variation (standard deviation) of grain size expressed by the circular diameter of its projected area by the average grain size]
has a monodispersity of 20% or less, an aspect ratio of 2.5 or more, and a particle size of 0.2 μm or more.

The composition of the hexagonal tabular grains includes silver bromide, silver iodobromide,
It may be either silver chlorobromide or silver chloroiodobromide. When containing legal ions, the content is 0 to 30 mol%,
The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. Further, it is preferable that the particles contain reduction-sensitized silver nuclei.

The silver halide grains can be produced through nucleation-Ostwald ripening and grain growth,
The details are as described in JP-A-63-151618.

In the silver halide emulsion used in the present invention, the crystal structure of the silver halide grains may be --like, the inside and outside may have different halogen compositions, or they may have a layered structure. These emulsion grains are described in British patent no.
No. 027,146, U.S. Patent No. 3,505,068;
No. 4,444゜877 and JP-A-60-143331
Disclosed in the issue etc. Further, silver halides having different compositions may be bonded by Evita kinial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

The silver halide emulsion of the present invention preferably has a distribution or structure in terms of halogen composition in its grains.

Typical examples are JP-B No. 4313162 and JP-A No. 61.
-215540, JP-A-60-222845, JP-A-6
These are core-shell type or double-structured particles in which the interior and surface of the particles have different halogen compositions, such as those disclosed in Japanese Patent No. 1-75337.

Moreover, it is not just a double structure, but also
It is possible to form a triple structure or a multilayer structure with more than that as disclosed in 2003, or to apply a thin layer of silver halide having a different composition to the surface of a core-shell double structure grain.

In order to give a structure to the inside of a particle, it is possible to create not only the above-mentioned enveloping structure but also a particle having a so-called bonding structure. These examples are disclosed in Japanese Patent Application Laid-Open No. 51-13354.
0, JP 58-108526, EP 199290A
2. Japanese Patent Publication No. 58-24772, Japanese Patent Publication No. 59-16254
etc. are disclosed. The crystal to be bonded can have a composition different from that of the host crystal and can be formed by bonding to an edge, part of a corner, or surface of the host crystal.

Such a bonded crystal can be formed even if the host crystal is uniform in terms of halogen composition or has a core-shell structure.

In the case of a bonded structure, it is naturally possible to combine silver halides, but it is also possible to form a bonded structure by combining silver halide with a silver salt compound that does not have a rock salt structure, such as silver rhodan or silver carbonate. Further, a non-silver salt compound such as PbO may also be used if a bonded structure is possible.

In the case of silver iodobromide grains having these structures, for example, in core-shell type grains, part of the core may have a high silver iodide content and the shell part may have a low silver iodide content, or conversely, part of the core may have a high silver iodide content. The grains may have a low silver iodide content and a high shell portion. Similarly, grains having a bonded structure may be grains in which the host crystal has a high silver iodide content and the bonded crystal has a relatively low silver iodide content, or vice versa.

In addition, the boundaries between particles with these structures with different halogen compositions may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to composition differences, or may be actively continuous boundaries. It may also be one with some structural changes.

The silver halide emulsion used in the present invention is EP-009672.
7Bl, EP-006441281, or DE-2.
The surface may be modified as disclosed in JP-A-60-221320, No. 306447C2. Even in such a case, the (100) plane / (
111) Surface ratio is measured.

The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, but as disclosed in JP-A-59-133542, the surface of the core of an internal latent image type emulsion can be obtained by selecting a developer or developing conditions. It can also be used for sensitization. Further, a light area latent image type emulsion covered with a thin shell can also be used depending on the purpose, and can be similarly applied.

When producing the silver halide emulsion of the present invention, the addition acceleration, amount, and concentration of silver salt solution (e.g., A g N O + aqueous solution) and halide solution (e.g., KBr aqueous solution), which are added to accelerate grain growth, are determined. A method of raising the temperature is preferably used.

These methods are described, for example, in British Patent No. 1°335.
No. 925, U.S. Patent No. 3. 672. No. 900, No. 3,650,757, No. 4.242.445, and JP-A No. 1983. -142329, No. 55-158124, etc. can be referred to.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of nitrogen ions present in the reactor to promote ripening. It is therefore clear that simply introducing a halide salt solution into the reactor can accelerate ripening. 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 addition of the silver and halide salts, or The above halide salts, silver salts, or peptizers can also be added and introduced into the reactor. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thionanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thionoanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in U.S. Pat. No. 2,222,264; 4
48. 534 and 3,320,069. Also, U.S. Patent No. 3,271,157;
Commonly used thioether ripening agents such as those described in No. 574.628 and No. 3,737,313 can be used. Or JP-A No. 5382408, No. 5
Thione compounds such as those disclosed in No. 3-144319 can also be used.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitation formation process. Such compounds may be initially present in the reactor or may be added along with one or more salts in accordance with conventional methods. Between US patents 2.
448. No. 060, No. 2,628,167, No. 3
, No. 737゜313, No. 3,772,031, and Research Disclosure, Vol. 134, 1975.
Halogenated compounds such as copper, iridium, lead, bismuth, cadmium, zinc, (chalcogenic compounds such as sulfur, selenium and tellurium), gold and compounds of group II noble metals as described in June 2013, 13452. The properties of silver halide can be controlled by making it present in the silver precipitation process. Special Publication No. 58-1410, Moiser (
Moisar et al., Journal of Photographic Science, Volume 25, 1977.19-27
As described on page 1, silver halide emulsions can undergo reduction sensitization of the interior of the grains during the precipitation formation process.

As mentioned above, the silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure No. 17643 and Research Disclosure No. 1871.
6, same No. 307105, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the three research disclosures mentioned above, and the relevant descriptions are shown in the table below.

Additive type RD 17643 RD 187
16 RD 3071051, chemical sensitizer 2
Page 3 Page 648 Right column Page 866 2 Sensitivity enhancer
Page 648, right column 3, spectral sensitizer, 2
Pages 3-24 Page 648 Right column Pages 866-868 Super sensitizer ~ Page 649 Right column 4, Sensitive white
Agent page 24, page 647, right column, page 868, 5,
Antifoggant, pages 24-25, page 649, right column 8
Pages 68-870 Stabilizer 6, light absorber, F Pages 25-26 Page 649 Right column
p. 873 Ilter dye, ~ p. 650 left column UV absorber 7, stain inhibitor p. 25 right column p. 650 left column to right column p. 872 p. 8, dye image stabilizer p. 25 650
Page left column 872 page 9, hardening agent page 26 65
Page 1 left column 874-875 pages 10, binder
Page 26, page 651, left column, pages 873-874, page 11, plasticizers, lubricants, page 27, page 650, right column, 876
Page 12, Coating aids, pages 26-27, page 650, right column, pages 875-876, surfactant 13, anti-static agent, page 27, page 650, right column 8
76-877 pages 14, Matting agent
pp. 878-879 In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 11.987 and No. 4,435,503.

Various color couplers can be used in the present invention, and specific examples thereof include the above-mentioned Research Disclosure.
(RD) No. 17643, described in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401゜752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1. 425. No. 020, No. 1,476.76
No. 0, U.S. Patent No. 3973.968, U.S. Patent No. 4,31
Preferred are those described in No. 4,023, No. 4,511,649, European Patent No. 249°473A, and the like.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
0,619, European Patent No. 4;351°897, European Patent No. 73,636, US Patent Box 3,061,432, European Patent No. 725. No. 067, Research Disclosure Nα2422 (June 1984), JP-A-1983-
No. 33552, Research Disclosure Nα24
230 (June 1984), JP-A-60-4365
No. 9, No. 61-72238, No. 60-35730,
No. 55-118034, No. 60-185951, U.S. Patent Box No. 4,500,630, No. 4,540.65
No. 4, No. 4,556,630, WO (PCT) 8
Particularly preferred are those described in No. 8104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent Box 4°052.212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4. 296. No. 200, No. 2,369
, No. 929, No. 2,801.171, No. 2,77
No. 2,162, No. 2,895,826, No. 3.
772. No. 002, No. 3,758,308, No. 4,334.011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121
．． No. 365A, No. 249,453A, U.S. Patent Box 3
, 446,622, 4,333゜999, 4,753,871, 4゜451.559, 4,427,767, 4,690,889 ,
Same No. 4. 254. No. 212, No. 4,296,19
No. 9, JP-A-6142658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in Research Disclosure Nα17643 Section ■-G, U.S. Pat.
No. 7-39413, U.S. Patent Box 4,004,929;
Same No. 4. 138. No. 258, British Patent No. 1,146
, No. 368 is preferred.

Couplers with appropriate diffusivity for coloring dyes include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,367.282, No. 4.409,32
No. 0, No. 4,576.910, British Patent No. 2,102
, 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
No. 57-154234, No. 60-184248, No. 63-37346, U.S. Patent No. 4,248,962
Preferably, those listed in No.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097, '140, British Patent No. 2,131,188, and JP-A-59-15763.
No. 8 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include U.S. Patent Box 4. 130. Competitive couplers described in US Pat. No. 4,283,472, US Pat. No. 4,338,393, US Pat.
Multi-equivalent coupler described in JP-A-60-18595
DIR redox compound releasing coupler, DIR coupler releasing coupler DIR coupler releasing redox compound or DIR letosox releasing redox compound described in No. 0, JP 6224252, etc., European Patent No. 173,3
Couplers that release dyes that turn yellow after separation as described in No. 02A, R, D, No. 11449, No. 24241, bleach accelerator-releasing couplers as described in JP-A No. 61-201247, etc., U.S. Pat. No. 4,553 Examples include couplers that release a ligand as described in JP-A-63-75747, and couplers that release a leuco dye as described in JP-A-63-75747.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,l-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid. Esters (triphel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, trifchlorohexyl phosphate, tri-2-ethylhexyl phosphate, tridotecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
ethylhexyl phenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl p-hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyl laurylamide, N-
(tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-dit
ert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl acelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl -2-butoxy-5-tertoctylaniline, etc.), hydrocarbons (paraffin, dodecylhensen, diisopropylnaphthalene, etc.), and the like. Further, as the auxiliary solvent, organic solvents having a boiling point of about 30°C or higher, preferably 5080°C or higher and about 160°C or lower, can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Etquin ethyl acetate and dimethylformamide are examples.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

Representative examples of color photosensitive materials to which the present invention can be applied include color negative films for general use or movies, color reversal films for slides or television, color positive films, and color reversal papers.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, k17643, page 28, and Nα18716, page 647 right column to page 648 left column.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and the film swelling rate TV2 is preferably 30 seconds or less.

The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate T'A can be measured according to a method known in the art. For example, Photographic Science and Engineering (A. Green) et al.
Pho, Sci, Eng, ), Volume 19, No. 2, 12
It can be measured by using a swellometer (swelling membrane) of the type described on pages 4 to 129, and 1% is 30% with a color developer.
9 of the maximum swelling film thickness reached when treated at ℃ for 3 minutes and 15 seconds.
0% is defined as the saturated film thickness, and is defined as the time required to reach this TIA film thickness.

The membrane swelling rate T% can be adjusted by adding a hardening agent to seratin as a binder or by changing the aging conditions after coating.

Further, the swelling rate is preferably 150 to 400%.

The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula (maximum swollen film thickness - film thickness)/film thickness.

Next, the processing method of the present invention will be explained.

In the present invention, desilvering treatment is performed after color development. Typical processing steps in the present invention are as follows.

■ Constant wearing of bleach bath ■ Bleach bath - Bleach-fixing bath ■ Constant wearing of bleach bath - Washing bath ■ Constant wearing of bleaching bath - Bleach-fixing bath Here, even if the number of bleaching baths and fixing baths is 1 tank, there should be at least 2 tanks. (For example, 2 to 4 tanks, in which case a countercurrent system is preferable).

In the method of the present invention, steps (1), (2), and (2) are particularly preferred.

The bleaching solution of the present invention has an oxidation-reduction potential of 150 as a bleaching agent.
Aminopolycarboxylic acid iron (I[[) complex salt with a voltage of mV or more is used. This compound is preferable to other oxides in terms of environmental protection, safety in handling, corrosion resistance to metals, and the like.

Below, aminopolycarboxylic acid iron (II) in the present invention will be described.
I) Specific examples of complex salts will be given, but the invention is not limited to these. In addition, the redox potential in the above definition will be described.

1, N-(2-acetamide) iminodiacetic acid iron (III) complex salt 1802,
Iron methyliminodiacetate ([[) complex salt 2003, iron iminodiacetate (II[) complex salt 2104.1.4
-butylenediaminetetraacetic acid iron (I[[) complex salt 2305,
Diethylenethioetherneaminetetraacetic acid iron (III) complex salt 2306,
Glycol ether diamine tetraacetic acid iron (II [) complex salt 2407,
1.3-Propylenediaminetetraacetic acid iron(II[) complex salt 250 Among these, particularly preferred are compound No. 7-1
．． 3-propylenecyaminetetraacetic acid iron(III) complex salt (
1,3-diaminopropanetetraacetic acid iron (also referred to as complex salt).

Aminopolycarboxylic acid iron (1) complex salts are used in the form of sodium, potassium, ammonium, etc. salts, but ammonium salts are preferred because they bleach the fastest.

Note that ethylenediaminetetraacetate iron (nu) complex salt (EDTA-F e (III)), which is widely used in the industry, has a value of 110mV, and diethylenetriaminetetraacetate iron (nu) complex salt (EDTA-F e (III)) has a
) complex salts and trans-1,2-chlorohexanediaminetetraacetic acid iron (1) complex salts are 80 mV, and are excluded from the present invention.

The bleaching solution in the present invention contains 0.2 mol/l of the bleaching agent.
The content is preferably 0.3 to 0.7 mol/l, more preferably 0.4 to 0.6 mol/l.

By setting the bleaching agent content within the above range, magenta and stain can be reduced.

However, the use of an excessively high concentration solution will actually inhibit the bleaching reaction, so the upper limit of the concentration should be 0. The amount is preferably about 7 moles.

Note that the concentration of the aminopolycarboxylic acid iron (III) complex salt preferably used in the present invention is also preferably within the above range.

Further, in the present invention, bleaching agents may be used alone or in combination of two or more kinds.

When two or more types are used together, the total concentration may be within the above range.

Furthermore, in the present invention, the redox potential is 150 mV.
In addition to the above bleaching agents, a bleaching agent with an oxidation-reduction potential of less than 150 mV may be used in combination. However, the amount used is preferably about 0.5 mole or less per mole of bleach having an oxidation potential of 150 mV or more.

Examples of such substances include ferric complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediaminetetraacetic acid, which have an oxidation-reduction potential of 150 mV or more, especially when used in combination with aminopolycarboxylic acid iron (III) complex salts. can be mentioned.

In addition, when using aminopolycarboxylic acid iron (1) complex salt in a bleaching solution, it can be added in the form of a complex salt as described above, but if the complex-forming compound aminopolycarboxylic acid and ferric salt (e.g. , ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate) may be present in the bleach solution to form a complex salt.

In the case of this complex formation, the aminopolycarboxylic acid may be added in a slightly excess amount compared to the amount required for complex formation with ferric ions, and when added in excess, it is usually 0.01.
It is preferable to use an excess in the range of 10% to 10%.

The pH of the bleaching solution of the present invention is preferably 5.5 to 2.5, and the preferable range for exhibiting the effect is 5.0 to 3.0, more preferably 4.5 to 3.5.

To adjust the pH within this range, organic acids such as acetic acid, citric acid, and malonic acid, as well as inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, can be used. 5
．． 5 (excluding aminopolycarboxylic acids, salts thereof, or metal complex salts thereof) are preferable in terms of imparting buffering properties to the region of the present invention; It can produce various organic acids such as acid, formic acid, butyric acid, malic acid, tartaric acid, oxalic acid, propionic acid, and phthalic acid. Among these, acetic acid is particularly preferred.

The amount of these acids used is preferably 0.1 to 2 mol, particularly 0.5 to 1. 5 mol is preferred.

It is preferable to add 3-diaminopropanetetraacetic acid to the bleaching solution in an amount slightly in excess of the amount required for complex formation with ferric ions, and the excess is usually in the range of 1 to 10%. preferable.

Furthermore, the bleaching solution of the present invention can also contain aminopolycarboxylic acid ferric complex salts other than 1,3-diaminopropanetetraacetic acid ferric complex salts, and specifically, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, Examples include ferric complex salts of acetic acid and cyclohexanediaminetetraacetic acid.

Various bleaching accelerators can be added to the bleaching solution 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.

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 11 bleaching solution.

Moreover, it is preferable to use ammonium nitrate as a metal corrosion inhibitor.

The amount of replenishment of the bleaching solution of the present invention is 50ml per 1-photosensitive material.
~2000ml, preferably 100ml~1100ml
0r? It is.

It is preferable to aerate the bleaching solution during the treatment to oxidize the ferrous complex salt of 1,3-diaminopropanetetraacetic acid produced.

After bleaching, the photosensitive material is then subjected to a fixing process using a processing solution (fixer solution and bleach-fix solution) having a fixing ability. As a fixing agent, sodium thiosulfate, ammonium thiosulfate,
Thiosulfates such as sodium ammonium thiosulfate and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, thioureas, thioethers and the like can be used.

Among them, it is preferable to use ammonium thiosulfate,
The amount is 0.3 to 3 mol per 11 of the fixer, preferably 0.
．． It is 5 to 2 moles.

In addition, from the viewpoint of promoting fixation, it is also preferable to use the above-mentioned ammonium thiocyanate (rhodan ammonium), thiourea, and thioether (for example, 3,6-cythia-1,8-octanediol) in the fixer. The amount of the compound is generally about 0.01 mol to 0.1 mol per 1 liter of the fixing solution, but the fixing promoting effect can be greatly enhanced by using 1 to 3 mol in some cases.

The processing solution with fixing ability contains sulfite as a preservative,
For example, sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite adducts of hydroxylamine, hydrazine, aldehyde compounds, such as acetaldehyde sodium bisulfite, can be included. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, and in particular, preservatives are described in JP-A-62-143048. It is preferable to use a sulfinic acid compound of Furthermore, JP-A-49-409
0.1 to 2 mol/l of the imidazole compound described in No. 43
It is preferable to use

The amount of fixer replenishment is 300ml per one photosensitive material.
to 3000rrl is preferred, more preferably 30
It is from 0ml to 1000rrl.

Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution 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.

Also, 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 JP-A-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 agitation speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the removal rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the acceleration results 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
It is preferable to have the photosensitive material conveying means described in No. 257, No. 191258, and No. 191259. As described in JP-A-60-191257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing deterioration in the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The effect of the present invention is remarkable when the total processing time is short,
Specifically, this effect is clearly exhibited when the total processing time is 8 minutes or less, and when the total processing time is 7 minutes or less, the difference from conventional processing methods becomes even more remarkable. Therefore, in the present invention, the total treatment time is preferably 8 minutes or less, particularly 7 minutes or less.

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)amino]aniline D-52-methyl-4-[N-ethyl-N-[β-hydroxyethyl]amino]aniline D-64-amino-3-methyl-N-ethyl=N −(β
-(methanesulfonamide)ethyltwoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenyl diamine 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-fluorinated diamine derivatives, Exemplified Compound D-5 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 g to about 20 g per 11 of the developer solution.
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 preferred amount added is 0.5 g to 1 g per 1f of color developer.
0g, more preferably 1g to 5g.

In addition, as compounds that directly protect the color developing agent, various hydroxylamines, Japanese Patent Application No. 18655/1982,
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. 61203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or No. 61-18
It is preferable to add various saccharides described in No. 0616. In addition, in combination with the above compounds, monoamines described in Japanese Patent Application Nos. 61-147823, 61-166674, 61165621, 61-164515, 61-170789, and 61-168159, etc. Class, same 6
No. 1-173595, No. 61-164515, No. 61
-Diamines described in No. 186560, etc., No. 61-16
No. 5621, and polyamines described in No. 61-169789, polyamines described in No. 61-188619,
nitroxy radicals described in No. 61-197760,
It is preferable to use the alcohols described in No. 61-186561 and No. 61-197419, the oximes described in No. 61-198987, and the tertiary amines described in No. 61-265149.

Other inspection agents 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-54-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
The aromatic polyhydroxy compound described in No. 746,544 and the like may be contained as necessary. Particularly preferred is the addition of an aromatic polyhydroxy compound.

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, trisodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium 〇-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 mol/l.
It is preferable that it is more than 0. 1 mol/l~0
．． 4 mol/I! It is particularly preferable that

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, transcyclohexanediaminetetraacetic acid, 1. 2-diaminopropanetetraacetic acid, hydroquine ethyl iminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenecyamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, l-hydroxyethylidene-1,1-diphosphone acid,
N,N'-bis(2-hydroquinbenzyl)ethylenediamine-N,N'-diacetic acid, two or more of these chelating agents may be used in combination if necessary.

These chelating agents may be added in an amount 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 pencil alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means that the developer solution 11 contains 2 ml or less, preferably not at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813,247, etc., p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50137726, JP-A-44-30074, JP-A-44-30074; Quaternary ammonium salts shown in No. 56-156826 and No. 52-43429, etc., U.S. Patent Nos. 2 and 4
No. 94,903, No. 3,128゜182, No. 4,23
No. 0,796, No. 3,253.919, Special Publication No. 1977-
No. 11431, U.S. Patent No. 2,482,546, No. 2
．． 596. 926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088,
No. 42-25201, U.S. Patent No. 3. 128. 1
No. 83, Special Publication No. 41-11431, No. 42-2388
3 and U.S. Pat. No. 3,532,501, etc., and other l-phenyl-3
-Pyrazolidones, imidazoles, etc. can be added as necessary.

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, 5methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Thiazolylmethyl-
Representative examples include nitrogen-containing heterocyclic compounds such as benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent brightener. As the fluorescent brightener, 4°4'-diamino-2,2'-disulfostilbene compounds are preferred. Addition amount is θ~5g/l, preferably 0.1g~4g/l
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 40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. It is preferable that the amount of replenishment is small, but it is 100 to 1500 mjl per rrr of photosensitive material!
Preferably it is 100 to 800 mf. More preferably, it is 100 ml to 400 ml.

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 can be a so-called black-and-white first developer used in the reversal processing of color photographic light-sensitive materials, which is commonly known, or a developer used in the processing of black-and-white light-sensitive materials. 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 black-and-white development, color development, bleaching, bleach-fixing, or fixing as described above.

Further, although a conditioning bath (or a bleach accelerating bath) may be provided between the color development and the bleaching solution, this conditioning bath can be omitted in the process of the present invention.

After the bleach-fixing or fixing process, processing steps such as washing with water and stabilization are generally carried out. Processing methods can 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,
It is possible to use disinfectants and anti-fungal agents (e.g. isothiazolones, organochlorine disinfectants, benzotriazole, etc.) to prevent the growth of various bacteria and algae, and surfactants to prevent dryness and unevenness. Wear. Or L,
E.

West, “Water Quality Cr1t
eria'', Phot, Sci.

and Eng., vol. 9. N(16, pa
Compounds described in ge344-359 (1965) 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 (e.g., formalin), a hexamethylenetetramine compound, a hexahydrotriazine compound, or an N-methylol compound described in JP-A-2-153348 may be used. I can do it. Formalin is not preferable from an environmental standpoint, and hexamethylenetetramine compounds, hexahydrotriazine compounds, and N-methylol compounds are preferable.

The stabilizing solution contains an ammonium compound, Bi,
Metal compounds such as AA, fluorescent whitening agents, chelating agents (for example, 1-hydroxyethylidene-1゜l-diphosphonic acid), fungicides, fungicides, hardeners, surfactants, etc. can be used. .

Further, the water washing step and the stabilization step are preferably carried out using 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 water used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to have a Mg concentration of 6 degrees Celsius or less than 5 .mu./l, or water that has been sterilized using 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 may occur due to evaporation, which is especially noticeable 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 flows into a pre-bath having a fixing ability.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, and the present invention is not limited thereto.

(Preparation of Sample 101) A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm, and designated as Sample 101. The numbers represent the amount added per d. Note that the effects of the added compound are not limited to the described uses.

1st layer/Antihalation layer Black colloidal silver seratin UV absorber U-1 UV absorber U-2 UV absorber L;-3 UV absorber U-4 UV absorber U-6 High boiling point organic solvent 01 2nd layer Intermediate layer gelatin compound Cpd-D High boiling point organic solvent Oi Dye D-4 Third layer/intermediate layer: fine-grain silver iodobromide emulsion with a puffed surface and inside (average grain size 0.06 μm, coefficient of variation 18%, 0.05 μm) 40g 0mg 0.1g 0.4mg 5g g 4g g g g g g Agl content 1 mol%) Seratin 4th layer: Low-sensitivity red-sensitive emulsion layer Emulsion A Emulsion B Seratin coupler C-1 Coupler C-2 Coupler C- 9 Compound Cpd-D High boiling point organic solvent 0i1-2 5th layer: Medium sensitivity red sensitive emulsion layer Emulsion C Gelatin coupler C-1 Coupler C-2 Coupler C-3 High boiling point organic solvent 0i1-2 6th layer High sensitivity red Sensitive emulsion layer Emulsion D Silver amount 0.05g 0.4 Silver amount 0.1g 0, 4 g 0, 8 g 0.15g 0.05g 0.05g 10 ■ 0, 1 g g g g 5g g g Silver amount 0 .4g Seratin l.

Coupler C-10゜Coupler C-30゜Additive P-10゜7th layer Intermediate layer Seratin O Additive M-10 Color mixing inhibitor CI) d -K 2゜UV absorber U-10゜UV absorber Shi- 60° Dye D'-10 8th layer, silver iodobromide emulsion with puffed surface and interior grain size 0.06μ
m, coefficient of variation 16%, content 0. 3 mol%) Silver content 0° Seratin
1゜Additive P-10 Color mixture prevention agent Cpd-J O.

Color mixing prevention agent Cpd-AO.

9th layer/low sensitivity green-sensitive emulsion layer g g mg g g 2g (average g1 2g g g g g Emulsion E Silver amount Emulsion F Silver amount Gelatin Coupler C-7 Coupler C-8 Compound Cpd-B Compound Cpd-D Compound Cpd-E Compound Cpd-F Compound cpa-c Compound Cpd-H High-boiling organic solvent 0i1-1 High-boiling organic solvent 0i1-2 1st O layer: medium-sensitivity green-sensitive emulsion layer Emulsion F Silver emulsion G Silver gelatin coupler C -7 Coupler C-8 Compound Cpd-B 0.3 g 0.2 g 0.5 g 0.05g 0.20g 0.03g 10 ■ 0.02g 0.02g o, 02g 0.02g 0, 1 g 0 .1g g g g g g 3g Compound Cpd-E Compound Cpd-F Compound Cpd-G Compound cpd-H High boiling point organic solvent Oi1-2 11th layer: High sensitivity green sensitive emulsion layer Emulsion H silver amount gelatin coupler C-4 Coupler C-8 Compound Cpd-B Compound Cpd-E Compound Cpd-F Compound Cpd-G Compound Cpd-H High boiling point organic solvent Oi1-1 High boiling point organic solvent Oi1-2 12th layer: Intermediate layer gelatin dye D-1 2 g 2g 5g 5g 1g g g g g 8g 2g 2g 2g 2g 2g 2g 0, 6 g O, 1g Dye D-2 Dye D-3 13th layer: Yellow filter layer Yellow colloidal silver Silver amount Ceratin color mixing inhibitor Cpd-A High Boiling point organic solvent 0i1-1 14th layer: Intermediate layer Gelatin 15th layer: Low-speed blue-sensitive emulsion layer Emulsion I Silver amount Emulsion J Silver amount Gelatin coupler C-5 16th layer: Medium-speed blue-sensitive emulsion layer Emulsion K Silver amount Ceratin coupler C-5 Coupler C-6 17th layer, high sensitivity blue-sensitive emulsion layer 0°0°0°5g 7g g g 1g 1g Emulsion L Silver amount Ceratin coupler C-6 18th layer: 1st protective layer Ceratin UV absorber U-1 UV absorber L'-2 UV absorber U-3 UV absorber U-4 UV absorber U-5 UV absorber L'-6 High boiling point organic solvent 0i1-1 Formalin scavenger pd-c pd-1 Dye D-3 19th layer, 2nd protective layer Colloidal silver Silver amount Fine grain silver iodobromide emulsion (average grain size 0°Agl content 1 mol%) Silver amount 0, 4 g 1.9 g 4 0 , 7 g g 4g 1g 3g 3g 5g 5g 2g 0, 2 g 0, 4 g 0.05g 0.1mg 06μm, 0.1g Seratin 0.4g 20th layer:
Third protective layer gelatin 0.4g polymethyl methacrylate (average particle size 1.5μ) 0.1g 4,6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5μ) 0.1g silicone oil
0.03g Surfactant W-13.0 ■ Surfactant W-20.03g In addition to the above composition, all emulsion layers contain additives F ~
1 to F-8 were added. Furthermore, in addition to the above composition, a ceratin curing agent H-1 and coating and emulsifying surfactants W-3 and W-4 were added to each layer.

Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol,
Phenethyl alcohol was added. 'CH.

6CH.

CH云π--１１１-いCH.

C) (Thea.

(t)C@? il.

C-9 0i1-1 dibutyl phthalate tricresyl phosphate pd-A H pa-i CH.

pa-c CH2CH2 pd C:H5 H H (t)C. H9 mC. H9 ■ o3K C. H.

So. to So, K SO3K 03Na -(CH2'-CHh CONHC,H,(t) Lid CH2-C juice- C00C,H.

HC,F, □802NHCH2CH,CH:OCH,CH
,N(CH3)CH2C00CH2CH(C2H5)C
,H.

Nap3S-CHCOOCH2CH(C2H,)C,H
.

The silver iodobromide emulsion used in H Sample 101 is as follows.

Monodispersed cubic particles, Fumi Nanako Suga, Tate Mia Spect Ratio: 4. O single n=
l”ift Daisai Tachiko, Hei E=I aspect ratio 7.0
Monodisperse cubic particles Monodisperse cubic particles Monodisperse cubic particles
Ratio 7.0 Monodispersed tetradecahedral particles Monodispersed cubic particles
Ratio 7.00.35 0.47 0.68 0.20 0.35 0.45 0.80 0.30 0.40 0.55 Table ■ (Preparation of sample 102) In the preparation of sample +01, emulsion A- The sensitizing dye L is added immediately before chemical sensitization, and the amount of chemical sensitizer is adjusted to achieve low sensitivity or maximum emulsions A, B,
For E-G, I, and J, after the particles were formed, they were desalted by the usual flocculation method, and then sodium thiosulfate, chloroauric acid, and potassium thiocyanate were added as chemical sensitizers at 70°C, and the mixture was stirred for 60 minutes. Then, chemical sensitization was carried out so that the fog was the lowest (or the sensitivity was the highest). Immediately thereafter, sensitizing dyes were added as shown in Table 1 at the same temperature, and after holding for 10 minutes, it was cooled.

After grain formation, emulsions C, D, H, and L were desalted by the usual flocculation method, and then treated with the following compound (A) as a chemical sensitizer, chloroauric acid, and potassium thiocyanate at 60°C. The mixture was stirred for 60 minutes, and chemical sensitization was carried out to achieve the highest sensitivity with minimal fog. Immediately thereafter, sensitizing dyes as shown in Table 1 were added at the same temperature, held for 10 minutes, and then cooled.

Sample 102 was prepared in the same manner as Sample 10 except that the concentration of compound (A) was also increased.

After processing the sample 101 prepared as above to a size of 35 m/m, a standard subject is photographed, and the following processing steps
Then, the cells were treated for 500 m, and the bacterial solution was used as a constant running solution.

Next, using the obtained running liquid, process step
Sample pieces of samples 101 and 102 subjected to internal optical wedge exposure of 50 CMS were processed and subjected to sensitometry.

The color reversal sensitivity of each color-sensitive layer was estimated based on the reciprocal of the exposure amount, which was 1°0 greater than the lowest density of cyan, macenta, and yellow.

The results are summarized in Table-2.

Next, prepare three sets of sample pieces of coating sample 10L 102,
One set was stored at 55°C and 230%RH for 3 days.
Another set was stored at 55°C, 280% RH for 3 days, and the remaining set was stored at room temperature as a control.
The film was developed and evaluated for incubation resistance.

Furthermore, three sets of sample pieces of coating samples 101 and 102 were prepared,
After performing wedge exposure at l/l00', one set is 50
Stored at 130% RH for 3 days, another set at 50°C
The samples were stored at 980% RH for 3 days, and the remaining set was stored in a freezer as a control, developed in the same manner as above, and evaluated for latent image storage stability.

The results are summarized in Table 3.

The bleaching time in processing step (2) was set to be equal to the desilvering performance (residual silver amount: 3 μg/crl) obtained by processing sample 101 in processing step (2), excluding the adjustment tower.

(Processing step ■) Processing process Time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38°C 1212, 21/m"th, water washing 2/l 3811 4〃 7.5 〃Reverse
2/l 38/ノ 4 //
1. l // Color development 61138/l12〃2
．． 2//adjustment 271 3811 4/l
1.1 Horn bleaching (A) 6
38 〃 6 ” 0.
15 Horn fixation 4// 38/l 8
/l 2,2 7゜Second washing (1) 21/38
1/4// Second washing (2) 2” 38” 4//7.
5 ll stable 2 no/
38 nol 4 l/1. l
〃Third washing 1 // 38 // 4
// 7.5 // The overflow liquid of the second water wash (2) was led to the second water wash tl) bath.

(Processing step ■) Processing process Time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38°CI21! 2.21/
m2 first water wash 2// 38tt 4tt
7j tt inversion 2” 38//4
” 1.1 '1 color development 6〃381
112112.2 Horn bleaching (B) 31/38116〃
0.151/Fixed 411 38/l
8 〃 2.2 〃Second washing (1) 2”
38"4""Second washing (2) 2/3
8 // 4 // 7.5 // Stable
2〃 3811 4 l/1. l
〃Third water washing 11'38'141-1
．． The overflow liquid of the 1'l second water wash (2) was led to the second water wash 11) bath.

The composition of each treatment liquid was as follows.

Nitrilo-N,N,N-trimethylenephosphonic acid 5-sodium salt 2.0g 2.0g
Diethylenetriaminepentaacetic acid 5 sodium salt 3.0g 3.0
g Potassium sulfite 30.0g 30
．． 0g hydroquinone potassium monosulfonate 20. Og 20.
0g potassium carbonate 33.0g
33.0g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.0g Potassium bromide
2.5g potassium thiocyanate
1.2g potassium iodide 2.0m
Add g 1. OA2.0g 1.4g 1.2g 2.0■ 1.0! pH (25°C) 9.60
A pH of 9.70 was adjusted with hydrochloric acid or potassium hydroxide.

Also, the same nitrilo-N,N,N-trimethylenephosphonic acid 5-sodium ram salt as the replenisher mother liquor and replenisher mother liquor. Og stannous chloride
Dihydrate salt 1. Ogp-aminophenol
0.1g Sodium hydroxide 8.0g
Add glacial acetic acid 15.0i water
1.01pH (25°C)
A pH of 6.00 was adjusted with hydrochloric acid or sodium hydroxide.

Color developer mother solution replenisher Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 2.0g Diethylenetriamine 2, Og Pentaacetic acid pentasodium salt 2.0g 2.0g
Sodium sulfite 7.0g 7.0
g Tripotassium phosphate dodecahydrate 36. Og 36
．． 0g potassium bromide 1.0g potassium iodide 90.0mg sodium hydroxide 3. Og 3.0g Notracic acid
1.5g 1.5gN-ethyl-
(β-methanesulfonamidoethyl)-3 methyl-4-aminoaniline sulfate 10.5g ]00
．． 5g36-dithiaoctane-1゜8-diol 3.5g 3.5g
Add water 1. M 1.07?
pH (25°C) 11.90 12
．． 05 pH was adjusted with hydrochloric acid or potassium hydroxide.

Weekly mother liquor Replenisher water 007nl Same as mother liquor Sodium sulfite 2g Sodium ethylenecyaminetetraacetate (trihydrate) 8g Thioglycerin 0,4-glacial acetic acid
Add 31rLl water and 1o
oOd week blood (A) Mother fluid Replenisher water 80W 8
00i Sodium ethyleneaminetetraacetate (trihydrate) 2g 2.9g
Iron ethylenecyaminetetraacetate (1) Ammonium (trihydrate) 120g 180
g Potassium bromide 100g 15
Add 0g water and get 100OTI! 10
0OJpH (25°(:) 6.0
The pH was adjusted to 5.4 using acetic acid or aqueous ammonia.

Warm blood (B) Mother liquid Replenisher 1.3-Noaminopropanetetraacetic acid 2.8g4.0g 1.3-Noaminopropane ferric ammonium acetate monohydrate 138. Og 207,
0g ammonium bromide 80.0g 1
20.0g ammonium nitrate 20.0g3
0.0g Hydroquinoacetic acid 50.0g
75.0g Acetic acid 50.0
g Add 75.0g water 1.
Off 1.01pH (25℃)
3,40 2.80 pH was adjusted with acetic acid or aqueous ammonia. Replenisher: Ethylenoaminetetraacetic acid, disodium, dihydrate, henzaldehyde, sodium bisulfite, ammonium thiosulfate (700 g/" n) Imitasol 1.7g 20.0g 15.0g 340.0J 28.0g Add the same water to the mother liquor 1.Of?pH (25°
C) 4.00 pH adjusted with acetic acid or aqueous ammonia Fixative solution A Replenisher ethylenenoamine and acetic acid Same as mother solution 2
Sodium salt/dihydrate salt 1.0g Charcoal carbonated sea urchin
6.0g compound, to”
Add 0.05 mol water to 1.0 f
pH (25°C) 7.50p I (adjusted with acetic acid or sodium hydroxide) Compound A'' C2H,OH Sodium salt/dihydrate 0.2g Hydroxyethylidene-1゜1-diphosphonic acid 0.05g Ammonium acetate 2.0g Sodium dodecylbenzenesulfonate 0.3 pH (25°C) 4.50 pH adjusted with acetic acid or aqueous ammonia did.

From the results in Table 2, the emulsion in which the sensitizing dye of the present invention was added before chemical sensitization was combined with the treatment containing ferric salt of l,3-diaminopropanetetraacetic acid as a bleaching agent (■). It can be seen that the sensitivity is high and, surprisingly, the macenta stain is also improved.

From the results shown in Table 3, it can be seen that the present invention is also a method for processing silver halide color photographic materials with excellent incubation resistance and latent image storage stability.

(Effects of the Invention) By carrying out the present invention, sensitivity can be increased and macenta stain can be improved, and incubation resistance and latent image storage stability can also be improved.

Claims (1)

[Claims] In a method of processing an imagewise exposed silver halide color photographic light-sensitive material with a bleaching solution after color development, at least one layer of the silver halide color photographic light-sensitive material is sensitized in an amount of 1 mmol or more per 1 mole of silver halide. Contains a silver halide emulsion chemically sensitized in the presence of a dye, and the bleaching solution contains an aminopolycarboxylic acid iron (III) complex salt with a redox potential of 150 mV or more as a bleaching agent of 0.2 mol/l or more. A method for processing a silver halide color photographic material, characterized in that: