JPH0312648A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow a rapid photographic processing by incorporating specific compds. into at least one layer of constituting layers. CONSTITUTION:This color photosensitive material contains at least one kind of the compds. expressed by formula I in at least one layer of the constituting layers. In the formula I, M denotes a metal ion; L denotes a bivalent org. group; Z denotes a quaternary ammonium group or a residual heterocycle which contains at least >=1 nitrogen atoms and in which the nitrogen atoms are quaternarized. The color photographic sensitive material which has no adverse influence on the photographic characteristics and allows a rapid bleaching or bleach-fix processing is obtd. in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material (hereinafter referred to as blade 2-
The invention relates to a color photosensitive material containing a heavy metal salt of a bleach accelerator suitable for rapid photographic processing, particularly rapid bleaching or bleach-fixing processing.

C. Prior Art] Generally, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. That is, the exposed silver halide color photographic material is subjected to a color development process. Here, silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former to provide a dye image. Afterwards, the photographic material undergoes a gold desilvering process. Here, the silver produced in the previous step is oxidized by the action of an oxidizing agent (commonly referred to as an S whitening agent), and then dissolved and removed by a silver ion complexing agent, commonly referred to as a fixing agent. Therefore, only dye images are produced in photographic materials that have undergone these steps. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process includes auxiliary steps such as maintaining the photographic and physical quality of the image or improving the shelf life of the image. Contains processes. Examples include a hardening bath to prevent excessive softening of the photosensitive layer during processing, a stop bath to effectively stop the entire development reaction, an image stabilizing bath to stabilize the image, or a stripping bath to remove the backing layer of the support. Examples include membrane baths.

In addition, the desilvering process mentioned above can be carried out in two steps, with the bleaching bath and fixing bath being separate baths, or it can be carried out in two steps, with the bleaching bath and fixing bath being separate baths, and in other cases, the processing process can be simplified for the purpose of speeding up processing and saving labor, and the bleaching agent and fixing agent can coexist. One step may be carried out using a bleach-fixing bath.

[Problem that the invention seeks to solve]

In general, red blood salt and ferrous chloride are good bleaching agents because they have strong oxidizing power.

However, the bleaching solution or bleach-fixing solution used as a red blood salt'fI bleaching agent releases cyanide through photodecomposition, which poses a pollution problem. I have to learn about it. In addition, the bleach solution using ferric chloride as a bleaching agent has a very low pH and a very strong oxidizing power, so it has the disadvantage that the parts of the processing machine that is filled with it are easily corroded.
There is a drawback that iron hydroxide in the emulsion layer is precipitated in the water washing process after bleaching and staining occurs.

On the other hand, potassium dichromate, quinones, copper salts, and the like have been conventionally used as bleaching agents, but these have the drawbacks of weak oxidizing power and difficulty in handling.

In recent years, from the viewpoint of rapid and simple processing and prevention of environmental pollution, ferric ion complex salts (eg.

Aminopolycarboxylic acid ferric ion complex salts, etc., and <Vc
The self-treatment method mainly using EDTA-iron (ill complex salt) is used for raw materials.

However, ferric ion/complex salts have a relatively low oxidizing power (because the bleaching blade is insufficient, the ones used as total bleaching agents are, for example, low-sensitivity silver halide colors made mainly of silver chlorobromide emulsions). When bleaching or bleach-fixing a photosensitive material, it is possible to achieve the desired purpose. When processing silver color photographic materials, especially color reversal photographic materials and color negative photographic materials that use high-silver emulsions, the bleaching effect may be insufficient, resulting in poor deplaning or problems with bleaching. It has the disadvantage of requiring a long time.

Persulfates are known as bleaching agents other than ferric ion complex salts, and persulfates are usually used as bleaching solutions in the form of chlorides. However, a disadvantage of bleaching solutions using persulfate salts is that they have a weaker bleaching blade and a significantly longer time to whiten than ferric ion/complex salts.

As described above, bleaching agents that do not cause pollution or corrosion of processing equipment have a problem in that they have weak bleaching blades and are not suitable for rapid processing. Therefore, it is desired to improve the color light-sensitive materials themselves so that they can be processed quickly even with bleaching agents with relatively weak bleaching properties such as ferric ion complex salts and persulfates.

A conventional method for this purpose is U.S. Pat. No. 3.77,020, i, to.

This is a method in which a bleaching accelerator such as an amino compound described in No. 163 is added to a processing bath (#white bath or bleach-fixing bath or a pre-bath thereof).

However, even with this method, it still takes a considerable amount of time to achieve sufficient bleaching, and most bleach accelerators do not exist stably in the bath or give off a foreign odor. There are problems in adding and using it.

In addition, JP-A-Sho also discloses a method for adding a known bleaching accelerator into color photosensitive materials! 3-7 Hiro 7! Conventionally known bleaching accelerators, which have been proposed in Publication No. λ, etc., have the disadvantage that they do not have a sufficient bleaching accelerating effect or that they have an adverse effect on the photographic properties of color light-sensitive materials.

Further, with this method, it is difficult to sufficiently bleach a color light-sensitive material containing a high silver content, such as a yellow filter layer or an antihalation layer, while preventing an increase in capri during storage due to the colloidal silver.

In order to improve these drawbacks, JP-A-67-Jf
Although a new bleaching accelerator has been proposed in No. JjjJ, it cannot be said to be sufficient for further rapid processing.

On the other hand, if conventionally known bleaching accelerators are directly contained in color photosensitive materials, they may cause harmful fogging, decrease sensitivity, or adversely affect photographic properties during storage (sensitivity, gradation, fog, etc.). ), as a method to overcome this problem, a method of adding bleaching accelerators as salts of all heavy metal ions has been proposed in JP-A-13-1989-3-Hiro, ≠ No. 30, European%.
Open to the public 3/7.2j'OAλ issue, 3/7. Tata/eight lambda
However, the effect of promoting bleaching in rapid processing cannot necessarily be said to be sufficient.

Therefore, the objects of the present invention are, firstly, to provide a color photosensitive material that can be rapidly processed; and secondly, a novel bleaching method that allows rapid photographic processing and does not adversely affect photographic properties. The object of the present invention is to provide a color light-sensitive material containing a heavy metal salt as an accelerator.A third object is to provide a color light-sensitive material suitable for rapid photographic processing, particularly rapid bleaching or bleach-fixing processing.

[Means to solve all problems]

The object of the present invention has been achieved by a color photosensitive material containing at least one of the compounds represented by the following general formula CI) in at least seven constituent layers.

General formula (I) 5-L-X (In the formula, M represents a metal, and in terms of appearance, silver, iron, cobalt, nickel, zinc, copper, rhodium, haladium, cadmium, iridium, platinum, gold, lead , thallium, cesium, and mercury.Metals of the Ib group, Ib group, and group II are preferable as M, and preferable examples include silver, zinc, cobalt, nickel, gold, copper, lead, and mercury.Particularly preferable examples include button. L represents a divalent organic group.

Divalent organic groups include alkylene, aryle/, alkenylene, ether, thioether, -CO--C8--C
(=NR)-(R represents a hydrogen atom or an optionally substituted alkyl group), -NR-(R represents a hydrogen atom or an optionally substituted alkyl group), a heterocyclic residue alone or Represents a divalent organic group composed of a heterocyclic ring.'C represents a saturated or unsaturated heterocyclic ring containing at least one nitrogen atom, oxygen atom, or sulfur atom; Pyridine ring, virol ring, imidazole ring, pyrazole ring, thiazole ring, oxazole ring, pyrimidine ring, pyrazine ring,
Pyridazine ring, thiophene ring, furan ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring.

Represents a pyrrolidine ring, piperidine ring, morpholine ring, and piperazine ring. This heterocycle may be benzofused.

This covalent organic group may be substituted with a substituent. Examples of substituents include alkyl groups, aryl groups, aralkyl groups, carboxy groups, sulfo groups, phosphor groups, phosphinic acid residues, hydroxy groups, amino groups that may be substituted with alkyl, ammonio groups that may be substituted with alkyl, and halogen atoms. , a nitro group, a carbamoyl group which may be substituted with alkyl, a sulfamoyl crystal which may be substituted with alkyl, an acyl group which may be substituted, an alkoxy group which may be substituted with It,
an optionally substituted alkoxycarbonyl group, an optionally substituted acylamino group, an optionally substituted alkylsulfonylamino group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonylamino group, an optionally substituted arylsulfonylamino group Good examples include arylsulfonyl groups. Preferred examples of L include alkylene, ether, thioether, -Co--C8--NR- (R represents a hydrogen atom or an optionally substituted alkyl group), and a heterocyclic residue alone or in combination. Examples of heterocyclic residues include thiadiazole and divalent organic groups.
Examples include a ring, an imidazole ring, a triazole ring, a tetrazole ring, an oxadiazole ring, a benzothiazole ring, and a benzoxazole ring, and particularly preferred examples include a thiadiazole ring and a triazole ring. Z represents a quaternary ammonio group or a heterocyclic residue containing at least one nitrogen atom, the nitrogen atom of which is quaternized.

It is quaternized by a quaternary ammonio group or an optionally substituted alkyl group or an optionally substituted aryl group.

The substituents are the same as those listed for L above.

The heterocyclic residue may be substituted, and the substituents are the same as those listed for L above. The heterocycle represents a heterocycle excluding the thiophene ring and the 7-ran ring among the heterocycles listed for L above. Z is an ammonio group quaternized with a lower alkyl group, or a heterocyclic residue containing at least one nitrogen atom and whose nitrogen atom is quaternized [for example, as a heterocycle, a pyridine ring, an imidazole ring, pyrrolidine ring, piperidine ring, morpholine ring,
[pi] is a radine ring] can be mentioned as a preferable example.

Particularly preferred is an ammonium salt quaternized with a lower alkyl group.An inorganic or organic anion is required as the counter salt of the ammonium salt. Examples include halogen ions, sulfate ions, nitrate ions, p-toluenesulfonate ions, methanesulfonate ions, and perchlorate ions.

Next, examples of compounds represented by the general formula CI' for use in the present invention will be given. However, the present invention is not limited to the following compounds.

■ 2. Ag5CH2CHzN(CH3)2・CI! O
4e 2H5 CH2CI420H CH3 CH3 H3 Regarding the method for producing the compound of the present invention, please refer to Tokko Sho! 7-irlr
For example, a 4-layer % gelatin aqueous solution RO1! Lt and bleach accelerator! It is obtained by mixing and stirring a metal nitrate solution and an equivalent amount of a metal nitrate solution.

The compound of the present invention may be contained in any layer on the support. Preferably, it is an intermediate layer and an antihalation layer, and particularly preferably an antihalation layer.

The amount of the compound of the present invention to be added may be any amount that exhibits the effect of promoting bleaching in the bleaching solution. It is preferably io"-6~/θ-2 mol/m2, and more preferably io-''~1o. −
3 mol/rn2.

The photosensitive material of the present invention has at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer, and a red color-sensitive layer on a support.
There is no particular restriction on the number and order of the silver halide emulsion layer and the non-photosensitive layer as long as [ is provided. 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. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the unit photosensitive layer is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation 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, DLR 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 German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer structure can be preferably used0
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-57-
No. 112751, No. 62200350, No. 62-20
No. 6541! As described in Japanese Patent No. i'162-206543, 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 1ii (BH) /
High sensitivity green photosensitive layer (G)/Low sensitivity blue photosensitive layer (G
L)/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (IIL), or B 11 / B L / G
L/G I (/R11/RL order, or a
ll/BL/GH/GL/RL/l? ) can be installed in the order of I, etc.

Furthermore, as described in Japanese Patent Publication No. 55-34932, from the farthest side from the support, the blue-sensitive layer/Gl(/
RH/GL/I? They can also be arranged in the order of L. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/Gll/R)I may be arranged in this order from the farthest side from the support. You can also do it.

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 disposed 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, the medium-sensitivity emulsion layer/high-density emulsion layer/low-density emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-speed emulsion layer / low-speed emulsion N / medium-speed emulsion layer,
Alternatively, the layers may be arranged in the following order: low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4.663゜2
No. 71, No. 4,705,744, No. 4,707,
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer.

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

When the photographic light-sensitive material of the present invention is a color negative film or a color reversal film, preferred silver halide contained in the photographic emulsion layer is silver iodobromide, silver iodo, containing about 30 mol% or less of silver iodide. Silver chloride or silver iodochlorobromide. Particularly preferred are silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

When the photographic light-sensitive material of the present invention is a color photographic paper, the silver halide contained in the photographic emulsion layer is composed of silver chlorobromide or silver chloride that does not substantially contain silver iodide. It can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Any silver bromide/silver chloride composition can be used for the halo 1 f composition of these silver chlorobromide emulsions. This ratio can vary widely depending on the purpose, but the silver chloride ratio is 2 mol%.
The above can be preferably used. For light-sensitive materials suitable for rapid processing, so-called high-salt emulsions with a high silver chloride content are preferably used. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, and 95 mol%
The above is more preferable. For the purpose of reducing the amount of replenishment of the processing solution, an emulsion of almost pure silver chloride having a silver chloride content of 98 to 100 mol % is also preferably used.

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) Nα17643
(December 1978), pp. 22-23, '1. Emulsion preparation and
types)”, and Nα18716 (I
November 979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Beaumontel (P, Glafk
tdes, Chests et Ph1sique
Photographique+ Paul Mont
el+ 1967), "Photographic Emulsion Chemistry" by Duffhn, published by Focal Press (G, F, Dufhn+Photo
graphic Emulsion Che+5is
try (Focal Press+1966)), Zelikman et al. [Manufacture and coating of photographic emulsions], published by Focal Press (V, L, Zelikmanet al,
, Making and Coating Photo
graphic Emul-sion 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 by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (I970); U.S. Patent No. 4
, 434.226, 4,414.310, 4,
433,048, 4,439.520, and British Patent No. 2,112,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. Furthermore, it may be bonded with a compound other than silver halide, such as Rodan oxide or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical training, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Nα1
7643 and Nα18716, 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 above two Research Disclosures, and the relevant descriptions are shown in the table below.

Attachment■n plate and■andL Shiguo J 1 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 sensitizer
Page 649 right column 4 Brightener Page 24 5 Anti-fog agent Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25, right column Page 650, 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 Page 650, right column 12 Coating aid, pages 26-27 Page 650, right column Surfactant 13 Static, page 27 Same as above Patch agent Also, photographic performance improvement with formaldehyde gas In order to prevent deterioration, US Patent No. 4,411.987 and US Pat.
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) i■17643, ■-C-G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4.022,620, No. 4.3
No. 26,024, No. 4.401.752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1.425,020, British Patent No. 1.476.760, U.S. Patent No. 3.973,968, Japanese Patent No. 4.314,
No. 023, No. 4,51L649, European Patent No. 249
, No. 473A, 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, U.S. Patent No. 3,061,432, No. 3725.067, Research Disclosure Oka No. 24220 (June 1984) month), JP-A-60-3
No. 3552, Research Disclosure Nα242
30 (June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 5
5-118034, 60-185951, U.S. Patent No. 4500.630, 4,540,654, 4,556,630, International Publication WO38104
Particularly preferred are those described in No. 795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent No. 4.052.212.
No. 4,146,396, No. 4.228.23
No. 3, No. 4,296,200, No. 2,369,9
No. 29, No. 2.801.171, No. 2,772.
No. 162, No. 2,895.826, No. 3.772
．． No. 002, No. 3,7511.308, No. 4.3
No. 34.011, No. 4,327.173, West German Patent Publication No. 3゜329.729, European Patent No. 121,36
No. 5A, No. 249°453A, U.S. Patent No. 3,44
6.622, 4,333.999, 4,7
No. 75,616, No. 4,451,559, No. 4,
No. 427.767, No. 4,690.889, No. 4
, 254.

No. 212, No. 4,296.199, JP-A-61-4
Those described in No. 2658 and the like are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure N [L17643
Paragraph ■-G, U.S. Pat.
No. 368 is preferred, and also US Pat.
, 774,181, which corrects unnecessary absorption of coloring dyes by means of fluorescent dyes released during coupling, and couplers that react with developing agents to form dyes, as described in U.S. Pat. No. 4,777,120. It is also preferred to use couplers which have a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity 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. 4.576910, British Patent No. 2.102.1
It is described in No. 73, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. A DIR coupler releasing a development inhibitor is the aforementioned IID 1764.
3. Patents listed in sections ■ to F, JP-A-57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, No. 63-37350,
U.S. Patent No. 4.248.962, U.S. Patent No. 4,782.012
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;
No. 2.131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the fluorescent material of the present invention include the competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. No. 4,310,618, DIR redox compound releasing couplers, DIR coupler releasing couplers, described in JP-A-60-185950, JP-A-62-24252, etc.
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜3
RoD, N(L 114
49, No. 24241, bleach accelerator-releasing couplers described in JP-A No. 61-201247, etc., U.S. Pat. No. 4,553
, No. 477, etc., Gantt release coupler, JP-A-6
Examples thereof include a coupler that releases a leuco dye described in US Pat. No. 3-75747 and a coupler that releases a fluorescent dye described in US Pat. No. 4,774,181.

The couplers used in the present invention can be introduced into the I5 light Lt F4 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.

Boiling point at normal pressure used in oil-in-water dispersion method is 175'
Specific examples of high boiling point organic solvents of C or higher include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amyl phenyl) phthalate, bis(2,4-di-t-amyl phenyl) isophthalate, bis(I,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid M (
triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphate, etc.), Benzoic acid esters (2-ethylhexylhenshade, dodecylhenzoate, 2-ethylhexyl-p
-hydroxyhenzoate, etc.), amides (N, S-
(diethyldodecaneamide, N,N-diethyllauryl, amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (stearyl alcohol, 2,4-d-tar t-amylphenol, etc.)
, aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl, 2-) (eg, 5-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like.

Further, as the auxiliary (6) agent, an organic solvent having a boiling point of about 30°C or more, preferably 50°C or more and about 160'C or less, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, Examples include cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

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

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO38100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-methyl p-hydroxybenzoate,
Phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2-(4-thiazolyl)
It is preferable to add various preservatives or fungicides such as benzimidazole.

The present invention can be applied to various colored fluorescent materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nα17643 and Nα18716
It is described from the right column on page 647 to the left column on page 648.

In the photosensitive 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, more preferably 23 μm or less, even more preferably 20 μm or less, and the film swelling rate Tlzz is The time is preferably 30 seconds or less, more preferably 20 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 TI/□ can be measured according to a method known in the art.

For example, Green et al., Photography Science and Engineering (PhoLogr, Sci, Eng.), 19
It can be measured by using a swellometer (swelling membrane) of the type described in Vol. 2, pp. 124-129, and T,
,, □ is defined as the saturated film thickness, which is 90% of the maximum swelling film thickness reached when treated with a color developing solution at 30° C. for 3 minutes and 15 seconds, and is defined as the time required to reach the film thickness of Tlzt.

The membrane swelling rate TI/□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD,
k 17643, pages 28-29, and Doma 1B716
615, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, but p-phinidine diamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline, 3-Methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochloric acid Examples include salts and p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-Nβ-hydroxyethylaniline sulfate is particularly preferred.

Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH 1 additives such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, hengimidazoles, benzothiazoles or mercapto compounds. It generally contains a development inhibitor or an antifoggant. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers. , an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, various calcinates such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, for example, Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,+I N-tetramethylenephosphonic acid, Typical examples include ethylenediamine di(0-hydroxyethyl acetic acid) and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The 9N of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
It can also be less than m1. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the volume of the processing liquid FIk (c+m) The above aperture ratio is preferably 0.1 or less, more preferably 0.001-0.05.As a method for reducing the aperture ratio in this way, In addition to installing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all processes such as bleaching, bleach-fixing, fixing, washing, and stabilization, and it is also possible to reduce the amount of replenishment by using means to suppress the accumulation of bromide ions in the developer. .

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately, or in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Depending on the purpose, treatment may be carried out in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. As a bleaching punishment, for example, iron (■), Kobal) (I
II), compounds of polyvalent metals such as chromium (Vl) and shell (■), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (I[l), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3 -Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Of these, iron ethylenediaminetetraacetate (I[
[) complex salt, and iron 1,3-diaminopropanetetraacetate (I
) fit salts and other iron aminopolycarboxylic acids (I[
I) Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleach or bleach-fix solution using these 7-minopolycarboxylic acid iron (Ill) complex salts is usually 4.0 to 8, but it can also be processed at an even lower pt+ to speed up the processing. .

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858;
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group as described in JP-A-53-124424, JP-A No. 53-141623, JP-A No. 53-28426, Research Disclosure No. Nα17129 (July 1978), etc.; Thiazolidine derivatives described in No.
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent No. 3,706,561
Thiourea derivatives described in No. 1, West German Patent No. 1,127,7
No. 15, the iodide salt described in JP-A-58-16,235;
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-42,434, 49-59,644, 53-
No. 94.927, No. 54-35.727, No. 55-2
Compounds described in No. 6,506 and No. 5B-163,940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,858.
No., West German Patent Tube No. 1.290,812, JP-A-53-9
Preferred are the compounds described in US Pat. No. 5,630, and also preferred are the compounds described in US Pat. No. 4,552,834.

These bleach accelerators may be added to the photosensitive material. 1. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for maximum shadows.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50'C, preferably 35°C to 45°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, it is preferable that stirring be as strong as possible. Specific methods for strengthening agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461, and the method of JP-A-62-183461. A method of increasing the stirring effect by using a rotating means, and further improving the stirring effect by moving the photosensitive material without bringing the wiper blade provided in the liquid into contact with the emulsion surface to create turbulence on the emulsion surface. method, and a method of increasing the circulation flow rate of the entire treatment liquid. Such agitation enhancement means include bleaching solutions,
It is effective in both bleach-fixing solutions and fixing solutions. Improved agitation speeds up the supply of bleach and fixing agent into the emulsion film,
It is thought that this increases the desilvering rate as a result. Also,
The agitation enhancement means described above are more effective when a bleach accelerator is used; 1. It is possible to significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by bleach accelerators.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable that the photosensitive material conveying means described in Japanese Patent Application No. 191259 be included. As described in the above-mentioned Japanese Patent Application Laid-Open No. 60-191257, such a conveying means can significantly reduce the carry-over of the processing liquid from the front bath to the rear bath, and is highly effective in preventing deterioration of 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 silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnat of the 5ociety
of Motion PicLure and
Te1e-visi'on Engineers 6th
It can be determined by the method described in Vol. 4, P, 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of color photosensitive materials of the present invention, as a solution to these problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, Hiroshi Horiguchi [Chemistry of antibacterial and fungicidal agents, (I986) Sankyo Publishing, Hygiene] Technical gold wire “Microbial sterilization, sterilization, and anti-mildew technology J (I982)
Industrial Technology Association, Japan Antibacterial and Antifungal Science Golden Wire “Encyclopedia of Antibacterial and Antifungal Agents” (
It is also possible to use the fungicides described in I986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14.850
No. 15,159, aldol compounds described in No. 13,924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can do.

In addition, l! of photosensitive materials! West German Patent No. 2, 22 for ff silver
6,770 or U.S. Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

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

Example-1 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material 10/ was prepared by applying layers having the compositions shown below.

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

(Sample 10/) No. tM; Antihalation layer black colloid coating Silver 0. /1 gelatin
0. Hiro 0 No. 21-; Middle class,! -G-t-Pentadecyl Hyde Akin/N 0. /1EX-/EX-j EX-/CoU-/-2-J HBS-/HBS-λ 3rd layer of gelatin (first red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide with mulch, Average particle size o
, tμ, variation image regarding particle size eL0゜/j
Silver o, rr sensitizing dye 1 a, ri x 10-” sensitizing dye 1
/, rXIO-5 sensitizing dye Ill
i, i×to 'sensitizing dye■
≠, 0X10-5EX-co
o, ir.

HBS-/0.00
jEX-/θ 0.0
λO7 0koOOkoro/ O Q O λ O Hiro gelatin /, λ0 μth layer (1st
No blue-sensitive emulsion) Tabular silver iodobromide emulsion (silver iodide 70 molt, average grain size 0.7μ, average aspect ratio!, J', average thickness O8,
2μ) Silver /, 0 sensitized color cumulative 1
r, /x10-5 sensitizing dye 11 /,
Hirox10-5 sensitizing dye ■ λ, 1xio
-'Sensitizing dye■ 3.01. jO"-
5EX-J O,4c00E
X-70,0IO EX-100,0/yo gelatin Ha30th! Layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide/1 molti, average grain size i, i
μ) Silver i, t.

Sensitizing dye ■ z, Hiroshi X10-5 sensitizing dye 1 /, ≠xio-5 sensitizing dye il
l x, 4cxio-'sensitizing dye■
1. /× 10-5 Silver iodide emulsion (silver iodide emulsion, average grain size o
, tμ, average aspect ratio t, o, average thickness o, iz>
Silver o, p.

Sensitizing dye V i, oxto-5 sensitizing color cumulative Vt t, oxto-' sensitizing dye ■
J-JrXlo-'EX-AO, λt
.

EX-10,oλ/ EX-7o, oi.

−≠Q /20 2 O 3 O, Q Hiro O O,020 0,00 Hiro o, r.

EX-It HBS-/HBS-Hiroshi gelatin 1st rI (second green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (iodide forceps, average grain size 0
．． 7μ, coefficient of variation regarding particle size 00it)
Silver o, t.

Sensitizing dye■ Ko, /×10"-5 sensitizing dye Vi 7.oXio-5 sensitizing dye■
λ, txio-'EX-60,/10 EX-40,010 EX-10,001 EX-70,0/koHBS-/0.760HBS-
Da o, oor gelatin
i,i.

2nd layer (3rd green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide lλ morch, average grain 02! 00 0 / O j diameter 1.0μ) Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX -4 EX-// EX-/ HBS-/ B5-2 Gelatin I/O layer (yellow filter layer) Yellow colloidal silver Silver O,0SEX-t
o, otrHB8-JO, OJ Gelatin 0. Wt 1st/layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (iodide #it morch, average grain size o, tμ, average surface area ratio!, 7, average thickness 0.lj
) Silver 0.24 as sensitizing dye■
3. jXlo-'silver/, ko J, jX10'5 r, oXio-5 7, OX/ 0''-4 o, otr O, 030 0, Oko taQ, ko! 0.10/, 7 HiroEX-ta o, rzEX-
40,/2 HBS-10,-t Gelatin / --2F 1st co-layer (3rd blue-sensitive emulsion layer) Monodisperse iron iodobromide emulsion (silver iodide 70 molt, average grain size o, rμ, grain size coefficient of variation O1/6)
Silver 0. ≠! Sensitizing dye ■ Ko, i×io-'EX-ta 0.20EX-100,0
/j HBS-10, o3 Gelatin O1 HiroΔ 13th layer (third blue-sensitive emulsion layer) Silver bromide emulsion (Silver iodide 14!-molti, average grain size 1
．． 3μ) Silver 0.77 Sensitized color cumulative■ λ, λX/ 0-'EX
-ta O,ko0HBS-/
0.07 gelatin
O-t 7th μ layer (first protective layer) Copper iodobromide emulsion (1 mol of silver iodide, 0.07 μ) Armor 0゜U-Hiroshi 0゜U-jQ.

HBS-/0゜gelatin
/.

1jth layer (λth protective layer) polymethyl acrylate particles (diameter/, rμm) S-/ -2 gelatin In addition to the above ingredients, each layer contains One or more surfactants were added.

O, Yuhiro0 , /j o,or O,7 Cogelatin hardening agent H Average particle size / l / 7 O O U-/ -j U-λ EX-/ R=C8H□7 U-φ (X/ 'l''''7/l (!Jim) (i) C4IsOCNH 1 EX-4 EX-7 EX-r EX-2 EX-1 0 8-/S-λ HBS-/; Tricresyl phosphate HBS-co Digtylphthalate HBS- to bis(2-ethylexyl)phthalate R=SCHCO
OCH3 CH3 EX-/ / ; Toward EX-/ However, R=H H-/ EX-/ λ CH2=CH-802-CH2-CONH-CH2CH
2=CH-802-CH2-CONH-CH2 Sensitizing dye ■ 2H5 U2) 15 (CH2) 3 SO3Na I ■ 2H5 2H5 ■ (CH2) 4 MOs Na Sample prepared as above/Ql no-ration prevention layer The following comparative compound f3X10 mol/m2 containing M
Sample 102 was prepared by adding gelatin dispersion to the sample. The comparative compound was produced in accordance with EP 3/7 No. 50.

``Similarly, exemplified compound 1.7.15.16.28f! X/
Added as gelatin dispersion so as to contain 0-'mol/m2, sample/Q3, IQ≠, 10J-110t
, 107.

Comparative Compound Samples These samples were cut into IJjmm widths, subjected to standard photographing of objects, and each JOm was subjected to running processing using a small cine developing machine under the following conditions.

Before and after the running process, the same sample is treated with a IIs element of jcMs at a color temperature ≠ t00, and the difference in blue transmission density before and after the running process (blue transmission density before the running process - blue transmission density after the running process) is expressed as an X-ray. The temperature was measured and calculated using a Wright JlQ photographic densitometer. Further, the amount of residual silver after the running treatment was measured by fluorescent X-ray method, and the results are listed in Table 1.

Processing method step Processing time Processing temperature Replenishment amount 0 Tank capacity Color development 3 minutes/j seconds 37.1r0C23-RI
All bleach 30 seconds 31r0C
rrnl /1 fixation (I) ≠! seconds
ir'c -ii constanty#(2) 4tt seconds
3r'C30Wtl/1 water wash (I)
, zo seconds 310C-/1 water wash (2)
JO seconds Jr'C3 (HRI ll stable 20 seconds 3r'C201tt /1
Drying 1 minute at 0C *Replenishment amount is per 3rmm width/m length Each process of fixing and washing was performed in a countercurrent manner from (2) to (I).

In addition, the amount of fixer brought into the water washing process in the above treatment is 1
jtm/m width of photosensitive material/m length.

(color developer) diethylenetriamine pentaacetic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamun sulfur acid salt a-(N-ethyl-N -β-hydroxye thylamino]-λ- Methylaniline sulfate salt add water H (bleach solution) /, 3-diaminopro Pan-ferric acid a mother liquor) ! , O Hiroshi, Q. 30.0 /, 3 /,,21ψ Ko, O μ, 7 Replenisher U) 6.0 j, O 37.0 0,5 3,6 6,2 /, ol io, o.

mother liquor U) /, 01 10, /j replenishment tu) ammonium water salt i,z-diaminopro pantetraacetic acid ammonium bromide ammonium nitrate Ammonia water (27%) Acetic acid (rit%) add water H (Fixer) sodium bisulfite Ethylenediamine tetrahedron acid disodium salt ammonium sulfite ammonium thiosulfate Aqueous solution <7oo11/1 Ammonia water (27%) add water H 7≠≠, O Ko, t r≠, O 17,5 io,.

Yo/,/ /, Ol ≠, 3 201.0 Hiroshi, 0 iI2o,.

2 evenings, O 1,! 71',0 /,Ol 3.4A Mother liquid U) Replenisher liquid) Yo, or r, O! , Oλ evening, O / co, Q co0.0 290.01d120 , 0141) 6.0al /r, 0yil /, 01 /, 01 4.7 6.7 (Washing water) Use common tap water for mother liquor and replenisher. H-type strongly acidic cation exchange resin (Am/(-Lite IR-/λOB) manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IRA- manufactured by Rohm and Haas)
Water was passed through a hot bed column filled with Hiroshi 01)) to reduce the concentration of calcium and magnesium ions to t3''9/it or less, followed by sodium incyanurate dichloride λQ
~/l and sodium sulfate iro/lk were added.

The pH of this solution is 4. , t-7,j.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit I) Formalin (37%) t, sml surfactant
Q-μCC10H21-0+CH
2CH20-), . H) Ethylene glycol
/, 0 triethanolamine λ,
Add O water /, 01 pHr,
0-7. .

As shown in Table 1 (Table 1), when the comparative compound was added, the amount of residual silver decreased to less than !μg/cm, which was within the allowable range, but the blue transmission density decreased significantly after running. On the other hand, the addition of the compound of the present invention showed that the amount of residual silver decreased significantly and the blue transmission density did not decrease much, and the desirable photographic performance remained stable at ℃ throughout the running. I can see that you are getting it.

Example-2 On a subbed cellulose triacetate film support,
Sample xoi, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is the amount of silver expressed in 9/m unit for silver halide, colloidal silver and coupler, and the mole of silver per mol of copper halide in the same layer for sensitizing dye. Shown in numbers.

1st layer: Anti-halation 1- Black colloidal silver Silver coating amount O, cogelatin
Co, Co UV-10, / UV-20,2 Cpd-io, ozSolv-
/ 0.0/5olv-20-01 So 1v-j O, 01 4th layer:
Intermediate fine particle silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0. /! Gelatin /・0cpa-co
O-2 third layer: first red-sensitive emulsion layer silver iodobromide emulsion (Agl 10-0 molti, internal high Ag
T type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 74<%.

l≠hedral grains) Silver coating amount O, corosilver iodobromide emulsion (Ag I Hiroshi, Q morch, internal high Ag
L-type, equivalent sphere diameter O0 Hiromu, coefficient of variation of equivalent sphere diameter 22%, l≠hedral particle) Gelatin ExS-/ ExS-λ ExS-J ExS-HiroExC-/ Silver coating amount 0.2 /, O Hiro ,! X10-' mole i, 5xio-' mole O0≠×io-' mole o, z×io-' mole 0.33 ExC-J o, ooy
ExC-J O, 0,
27ExC-10,7 Hiro layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Agl / 6 mmol, internal high Agl type, equivalent sphere diameter /, θμ, coefficient of variation of equivalent sphere diameter 2j%, plate shape Particles, diameter/thickness ratio, 0) Silver coating amount 0.5! Gelatin □, 7Ex8-no
JXlo-'Ex8-ko
/X/C)”Ex8-i
o, 1xto-'E, xS-a
o, JX/o-'ExC-J
o, oriExC-Hiroshi o,i.

ExC-6o, oi Layer 3: Third red-sensitive emulsion layer Silver iodobromide emulsion (Ag (I0.0 mol, internal high Agl type, equivalent sphere diameter 7.2μ, coefficient of variation of equivalent sphere diameter λ1%, Plate-shaped particles, diameter/thickness ratio t, θ) Silver coating amount O, Tagelatin o, tpExS −/
, 2X10-'ExS-s
o, JXlo-'ExS-J
O, 2×10'ExC-Hiroshi
0.07ExC-tO,
048o1v-/0. /λ5ol
v-J O, /2 6th layer: Intermediate layer gelatin /・0 cpa-40, / 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (Agl 10.omol, internal high Ag
L-shape, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter L /≠hedral grain) Silver coating amount 0.2 Silver iodobromide emulsion (Agi Hiroshi, Q molar 俤, internal height AgI
Type, equivalent sphere diameter □, Hiroμ, coefficient of variation of equivalent sphere diameter I, amount of silver coated on hehedral particles 0. / l, 2 rxi o”-' λ×/θ-4 ixio-' 0, Hiro 1 0, i.

o, oi O, cogelatin Type, equivalent sphere diameter/, 0 μ, coefficient of variation of equivalent sphere diameter IJ, plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount o, t gelatin. , 3jE x S
-r x8-4 xS-7 ExM-/ ExM-J Solv-/ Second layer: Intermediate gelatin 1st O layer: Third green-sensitive emulsion J- Silver iodobromide emulsion (Agl 10.0 mol, internal height Ag
l-type, equivalent sphere diameter/, λμ, coefficient of variation of equivalent sphere diameter it%, plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount l, O Q, r koX10''''40, r×10 -' 0, rxlo-' o, oi O, Q HiroQ,! J, JXlo-' /, 4CX/J-4 0, 7X/Q-4 0, Qrio, oi O, /! Gelatin E x S -z xS-A ExC-1o, oo z 8o1v-10, 11th layer: Yellow filter layer cpci-j O, Or gelatin 0.'8o1v- /
0. /First layer: Intermediate layer gelatin 0. jCpd-20,
/ No. 137 @: 7th blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mole, internal high iodine type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter/e%.

/particulate particle) Silver coating amount 0. / Silver iodobromide emulsion (Agl Hiroshi, O Morch.

Internal high iodine type, ball equivalent diameter 0. Reference μ, The coefficient of variation of the equivalent sphere diameter is 2 kochi, l≠hedral particle) Silver coating amount o, or gelatin xS-1 ExY-/ ExY-2 Solv-/ 1st μ layer: λth blue-sensitive emulsion layer Silver iodobromide emulsion (AgI).

Internal high AgI type, equivalent sphere diameter/coefficient of variation of equivalent sphere diameter/A%, /prohedral particles) Trowel application amount/, 0 3'1.10-' Q,! 3 0.02 Q, / TaOmolti1, Oμ, Gelatin xS-4 ExY-/5olv-/ No. irf@: Intermediate layer fine grain silver iodobromide (Ag uniform type, equivalent sphere diameter Q Gelatin O0/R0 , J 2×10" 0.2 2 0 + O7 1,2 molten 1.73 μm Coating with a trowel 1st layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI /≠ , Omole, internal height Ag
Type I, equivalent sphere diameter i, rμ, coefficient of variation of equivalent sphere diameter 2t%, plate-like particle, diameter/thickness ratio!
, O) Silver coating amount i,.

Gelatin O-! ExS-4/,
rXlo-' ExY-10,2 8o1v-/ o, oy 17th layer:
First protective layer gelatin /°t UV-10,7 UV-ko O,ko8o1v-/
0.0/5olv-λ
o, oi 1st r layer: λth protective layer fine grain silver bromide (equivalent sphere diameter 0.07 μ) Silver coating amount o, ir Gelatin 0.7 polymethyl methacrylate particles (diameter /, 5 μ) W-/H -/ cpci-t UV-1 UV-2 xM-3 xC-6 0 cooc summer I.

x/y=7/3 (weight ratio) xC-1 xC-5 C+il(zs EχM 2 xM-4 xS-2 xS-3 C□H3 C Yi H.

xY-1 xY-2 xS-1 pd-3 ExS-6 C-Hs ExS-0 p d-5 -1 olv-1 -1 CHz -CH5Oz CHt C0NH-CHICH
z -CH5Ch CHHz C0NHCHz Processing method Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes/! seconds jr'c 20rnl
jtl bleach constant 5W 3 minutes oo seconds 3r0C30TR1
! 1 piping type.

Washing with water (2) 20 seconds 3j'C1Onl 21
Stable 25 seconds 3'C2θd Col dry
Drying: 0 seconds 6 t'c Replenishment amount: 31 mm width/m length Next, write down the composition of the treatment solution.

(Color developer) Mother solution J) Replenisher U) Diethylenetriaminepentaacetic acid l-hydroxyethylidene/,/-diphosphonic acid Sodium sulfite Potassium carbonate Co, 0 2.2 J, (7 3,2 ≠, O Hiroshi, G30. 0 37.0 Potassium bromide /,μ O-≠potassium iodide 1.Yu■ -Hydrokifluamine sulfate λ,≠ 2.Rhiro-(N-
Ethyl-N-β-hydroxyethylamino)-λ- methylaniline sulfate ≠mj 4.
j Add water /, Ol /, 01
pH10.0! 10. /r (Bleach-fix solution, mother liquor, replenisher common unit i) Ethylenediaminetetraacetic acid ferric ammonium dihydrate ioo.

Ethylenediaminetetraacetic acid! , 0 ammonium sulfite 20.0 ammonium thiosulfate aqueous solution (7 (7%) 3θ0, 0 ml acetic acid, water added /, 01 p Hl-,.

(Stabilizing solution) Mother liquor, replenisher common unit J) Formalin (37%), oml polyoxyethylene-p-monononylphenyl ether (average degree of polymerization io) o, i.

Ethylenediaminetetraacetic acid disodium salt 0.02 Add water /, 01 pH 1,0-1! , 0 (washing water) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-/CoQB, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-μ00, manufactured by Rohm and Haas). Water was passed through a packed hotbed column to reduce the concentration of calcium and magnesium ions to 3 da/l or less, and then sodium incyanurate dichloride 20 m9/l and sodium sulfate 0. /! g/no was added. The pH of this solution is 6. !
~7°! within the range of

Comparative compounds similar to those described in Example-1 were added to the antihalation layer (first layer) and the second layer of the sample Koi prepared as described above in accordance with Example 1, respectively. This was designated as sample 202.

Next, similarly, exemplified compound 1.7.15.16.28.33
was added, and samples λ03, λO Hiro, -〇! , KoQ6.20
71.2or was produced.

These samples were cut into 3mm wide pieces, used for photographing standard objects, and each piece was separately subjected to running processing in 1Qm portions using a small cine developing machine under the following conditions.

Before and after the running process, the color temperature ≠ r00 was applied to the same sample.
- Processing with CM8 exposure, measuring the difference in green transmission density before and after (green transmission density before running process - green transmission density after running process) using an X-Rite 310 type photographic densitometer; Calculated.

Further, the amount of copper remaining after the running treatment was measured in the same manner as in Example 1, and the results are shown in Table 1.

Table 2 (Effects of the Invention) The color light-sensitive material of the present invention has no adverse effect on photographic properties (and can be rapidly bleached or bleach-fixed).

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material, characterized in that at least one of the constituent layers contains at least one compound represented by the following general formula [I]. General formula (I) MS-L-Z (wherein M represents a metal ion, L represents a divalent organic group, and Z represents a quaternary ammonio group or at least one nitrogen atom containing the nitrogen atom) represents a quaternized heterocyclic residue.)