JPH0467037A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain stable photographic performance in continuous processing by processing the silver halide color photographic sensitive material containing a specified compound with a color developing solution containing a water-soluble polymer comprising repeating units each having an anionic group. CONSTITUTION:The silver halide color photographic sensitive material contains in at least one layer the compound represented by formula I in which each of R1 and R2 is independently 1 - 18 C alkyl or alkenyl and each of R3 and R4 is independently 1 - 18 C alkyl. This photographic sensitive material is processed with the color developing solution containing the water-soluble polymer comprising the repeating units each having the anionic group and other repeating units derived from another monomer in a molar ratio of 10-100 : 90-0, preferably, 30-100 : 70-0, thus permitting variation of photographic performance in continuous processing to be reduced.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a method for processing color photographic light-sensitive materials, specifically, superior processing stability and preservation of color images. The most important thing...This article concerns the processing method for Rogge/chemical complex color Yoshin light-sensitive materials.

(Prior Art) The fastness of the colored image 11 is in accordance with the basic properties desired for the pigment image formed by the reaction between the My/Ta coupler and the oxidized product of the color-forming herbal medicine.

The fastness of color images from special K and magenta couplers to W types is not satisfactory, and several means have been proposed to improve this light fastness.One example is the use of ultraviolet absorbers. The color image can be completely protected from ultraviolet rays by using anti-fade agent, the color image can be completely prevented from fading by the source, and the magenta coupler can be lightfast? A method has been proposed to introduce a grant fund.

Among these methods, the method using an ultraviolet absorber is certainly effective, but in order to impart satisfactory light fastness to the color image, a relatively large amount of ultraviolet absorber is required. In this case, there is a disadvantage that the white area of the colored area is contaminated due to the coloring of the UV absorber itself. There is a limit to the hardening of tiij* using ultraviolet absorbers, which cannot prevent color fading.

The introduction of a group that imparts needle-like properties to the magenta coupler has led to an increase in the cost of sweet acid due to the increase in the coupler acid step, the difficulty of synthesis, and the synthesis yield. It is difficult to obtain a satisfactory condition only with the coupler that has been introduced.

Are these UV absorbers light resistant? Even with the introduction of the imparting group 9 into the Mase/Ta coupler, in order to balance the light fastness with other/an and yellow color images, it is no longer necessary to supplement it in the f of the anti-fade agent. Ru. As a method of using anti-fading agent, phenol water injection al! Base U7J
[IrL'''C] There is a known method in which all antifading agents contain a group that produces a phenol hydroxyl group by decomposition of water. Examples of such antifading agents include phenol hydroxide,
Bisphenol, Tocopherol, Hydroxy/:
A number of proposals have been made, including /4-isomers, hydroxychroma/vesicles, and bisspirochromans. However, although these are known to completely prevent discoloration and fading of magenta color, they cannot be said to be effective against light.

! fc, changes in photographic performance when used in large quantities (maximum
This tends to cause problems such as a decrease in # and a softening of the hierarchy.

For example, as a method to improve this 't''L,
No. 44117/ discloses the use of hydroquinone ether compounds in combination. If you go to the compound of this inn, you will find the US% X Hiroshi, -5 Hiroshi, Ko/No. 6, and the Japanese Patent Application Publication No.
! It has been reported in issue 3, etc. It is true that the combined use of these compounds with magenta couplers has been found to improve the discoloration and fading of color images, but it has been found that the use of these compounds in combination with magenta couplers has been shown to improve the discoloration and fading of color images. Difficulties in implementing stable photographic performance, particularly the processing that can be obtained for magenta color images, have become an emerging problem.

10,000, we improved the minimum density (L)minJYastin of the white background part of the unfinished part, and the photographic property I which is stable over a long period of time!
! As a processing method for silver halide color photographic light-sensitive materials (hereinafter referred to as "color light-sensitive materials") that gives A color-forming dust image composed of the above-mentioned silver chloride emulsion, containing a polystyrene sulfo/acid derivative in the color-forming developer solution, containing at least 13° It is disclosed that it is processed in
! 7t! g42- / OJ j j r No. VC*
, all 9 radiation/yo/prevention dyes added to color g+uu! Polystere/Sulfo/#
Guidance? It is disclosed that the coloring dust image processing method used in the production process can be used to achieve the above-mentioned purpose.

While magenta and a 7'jk degree,
Concerning the minimum concentration (Llmin, ) and maximum concentration (DmaX) in maze/me plexus ￥C, it is clear that the vibrations are large in rapid processing. It was found that this is a problem that needs to be improved.

(Problem to be solved by the invention 9) Therefore, the purpose of the present invention is to improve the light fastness of color lfl images,
Processing blade e? for halogen/silver oxide color photographic light-sensitive materials that maintains stay/prevention of uncolored areas and provides stable photographic performance in continuous processing. f.

(Means for solving the problem) As a result of extensive research, we determined that the above objective could be achieved by implementing the following method.

In a method of processing a halogenated complex color photographic light-sensitive material after exposure with a color developing solution containing an aromatic 7th class amine color fading agent, at least the... At least 7 layers are coated with the following general formula CI) / Haloke made by the following general formula CI) / A silver oxide color photographic light-sensitive material is added to the color development Toru Tsuka at least / 115 Anio / At least /a [? This can be achieved by processing a Rogge/Silver Cide color photographic light-sensitive material, which is characterized by processing with a color developing solution containing M.

-Formula (I) In the formula, R and R2 may be the same or different, each having a carbon number of / to /r, a straight chain l or branched υ alkyl group, or an alkenyl group kv ``3 and R4 may be the same or different Also, each moxibustion tree has a power of 1 to 1;

Zarani, color development process wheat, Momochi's desilvering process blade, which performs 6 processes, and also the processing method 5, which is characterized by using the overflow version of Etsu silver process precepts, is also uniformly ash. I was able to do it.

Hereinafter, before explaining the present invention in detail, the compound represented by formula (I) in Table t) will be explained.

In the formula, and R2 are straight chain or branched alkyl groups having carbon number / to /r (for example, methyl, ether, n-10
Bill, l-propyl, n-butyl, 5ec-butyl, l
-butyl, 1-butyl, Loebe/chill, t-innal,
rhohexynol, 5ec-hex/l, -1hex/l, rhoofnal, t-octyl, 2-ethylhexyl, n-nonyl, nonyl, Ω-te/l, l-denle, n-dodenle, rhotetradenle, n- hexadecyl, n octade/
alkenyl group (for example, 1-propenyl, allyl, stearenyl group), and R4 is the number of carbon atoms /
The I chain lt of /l is a branched alkyl group (R1 and R2
with the alkyl group shown in )? Sixty guns.

Below is a list of compounds that are represented by the general formula (1), but the invention is not limited to these compounds. Compounds that can be synthesized by people can be prepared by the method described in Japanese Patent No. 2, No.

The compounds represented by the general formula (1) of the present invention can be conveniently incorporated into any layer constituting the color photosensitive material. When used for a silver halide photosensitive layer, coupler 1 of that layer
It is preferably used in an amount of from 10 to 3 mol per mole, but preferably from 2 to comole. When used in a non-photosensitive layer, it is in an amount of from zxio to It. Preferably non-lII!, 1x per party layer
The amount of io-2 to /f.

The compound represented by the general formula (1) of the present invention is preferably used in the non-#LC-based layer in contact with the silver halide photosensitive layer, but more preferably in the green-sensitive emulsion layer. It is a non-evil source layer that is in contact with Seven II.

Two or more of the compounds represented by the general formula (1) of the present invention can be used in combination, they can be divided into different layers, or different compounds can be used depending on the purpose.

It is also possible to disperse and use the compound represented by the general formula (1) in a high-boiling point single solvent as described below, coexisting with couplers and other hydrophobic compounds, or use the compound dispersed alone.
- You can use it.

Next, details of water-soluble polymers containing repeating units with an anionic foundation of at least %/piece of uninvented JIB
K.Explain. The anionic functional group of the present invention includes -C
O014 group, -sc+, h group, -80 Hit, -0
P+(J)i) 2 groups (!fc is the monoalkyl ester group -oSu3h group, etc.).
For example, it may be in the form of an ammonium salt (for example, a salt with ammonia, methylamine, dimethylamine, etc.).

The pH values of ethylenically unsaturated monomers having such anionic functional groups are shown below, but are not limited thereto.

C) 12=CH C0 (JC) I C) 1 (JCOC) l, CH, C0
0)1C)12=C)1 coo←CH27CCj(JH C)12=C)i C(JN)11CH2+3cuuh ch2=ch (,:CIN)i←ch,su5C(J(J)1H3 CB.

CH3 C) i2=C COOC) 12C) (20803H The polymer containing M repeating units containing at least 17 anionic functional groups of the present invention may be a monopolymer or may be engineered to contain anionic functional groups. It may be a copolymer containing at least the same amount of monomers.

The primary water content of the polymer may be a copolymer with another ethylenically unsaturated polymer within a range that provides solubility in an alkaline aqueous solution.

Examples of this series of copolymerizable ethylenically unsaturated polymers include esters derived from acrylic acids such as acrylic acid, α-chloroacrylic acid, and α-alkyl acrylic 112 (target is methacrylic aI, etc.). Especially Abad (for example, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, comethoxyethyl acrylamide, diacetone acrylamide, mesol acrylate, ethyl acrylate, r-propyl acrylate, n-7' tyl acrylate, t-butyl acrylate, 1so-butyl acrylate, -mono-etherhexyl acrylate, o-octyl acrylate, lauryl acrylate, methyl methacrylate, methyl methacrylate, n-methyl methacrylate, cyclohexyl methacrylate, co-hydroxy ether acrylate, co-hydroxyethyl methacrylate, β-
Alkoxyethyl (meth)acrylates (e.g., cometquin ether acrylate, comethoxyethel methacrylate, comethoxyethel acrylate, J-
Ethkyne ethyl acrylate, co-ethoxy ether methacrylate, -1-butoxy ether acrylate, -1-rhoprobyloxyeder methacrylate, co-(co-methoxy) ethoxy ethyl acrylate), β-sulfonamide ether (methanoacrylate, β-cal i)
β-sulfonamide ethyl (meth)acrylate, β-alkoxyethyl acrylamide (the alkoxy group contains a plurality of substituted alkoxy groups), β-sulfonamide ethyl acrylamide, β-caramide ethyl acrylamide ], vinyl ester (FPJ, t
l-1i! lll: vinyl acid, vinyl laurate, acrylonitrile, methacrylate, dienes (IF
butadiene, isoprene), aromatic vinyl compounds (styrene, divinylbenzene and its derivatives, vinyl toluene/, vinyl acetophenone, vinylidene chloride, vinyl alkyl ethers (Nll)
: vinyl ethyl ether), maleic acid ester, N-
Vinylcopyrrolidone, N-vinylpyridine, Okobi λ-Okobi≠-vinylpyridine, ethylene, Propyridine/
, /-buty/, imbutene, and the like.

Preferred among these monomers are those which themselves or their homopolymers are soluble in water or alkaline water baths.

The copolymerization ratio of repeating units containing anionic groups and repeating units derived from other monomers may vary depending on the polarity of the monomer components used; The repeat unit preferably ranges from 10 to 100 moles, more preferably from 30 to 100 moles.

The production of the compound @r@ of the present invention is carried out using a polymer containing an anionic group and, if necessary, other compounds ti! It can be carried out using conventional radical polymerization methods (solution polymerization, suspension polymerization, emulsion polymerization, precipitation polymerization, dispersion polymerization, bulk polymerization, etc.) using sound.

Below, preferred water fIII of the present invention! ! 1: This refers to a heavy material, but the present invention is defined in this way.
(The copolymerization ratio in the indicated compound is expressed as a molar ratio.)

The degree of polymerization of these compounds is 100-! 1000 is preferred, and 300 to JOOOCQ@ is particularly preferred.

p-/ ←C) 12C) fsooH H3 P-λ ←C) 12C sooH -j fcH2CHC0(JCHC1((7COC)I, CH2C00KH
3 -j (C)12C) isuC(JNHeCH,su5COONJI x/y=rij/j x/y = 7j/λj x/y = j O/ j 0 x/y = j O/ j 0 x / y / z = ! 0 / 2 j / ko5
x / y = J Q / 70 CH3 H1 X / y = j O / j 0 The color printing material of the present invention has the above-mentioned at least It is treated with a color developing solution containing a water-soluble polymer having a superfunctional repeating unit.

The amount added to the color development of the water-bathable polymer containing repeating positions containing at least 1% of anionic groups [1i] is
The coloring lAgl solution/l is set in the range of 0.0/-102. 0.0/f↓If there is less, the effect of the present invention is small<, 1
If it exceeds 7t, 10tt-, it is largely due to physical factors such as it takes a lot of time to prepare the color developing GL solution in terms of solubility, and the viscosity of the fixed color developing GL solution increases after being prepared. 17t, 10? If the amount exceeds 100%, the effect of the present invention will be nearly saturated, and even if the amount added is increased, the increase in the effect will be small.

The uninvented water-soluble polymers can be used in combination.

The water solubility of the water-soluble polymer of the present invention is defined as 0.01 t/I or more being uniformly dissolved in distilled water/l of λz@C. It is a method of adding a constant amount of t, 1st, and thick molten iron, but it is best to apply the weight at the beginning.

Furthermore, the present invention uses a color development process vk1 [and then a desilvering process is carried out'5, but from the viewpoint of environmental conservation, it is desirable to perform these desilvering processes as well, such as recycling, to reduce the amount of waste liquid!' nru. However, in a process in which the color dust image frame is low light supplemented and the bleach-fix solution is also regenerated, the fatigue of the six solutions is large, and the accumulation @J%l increases.

Therefore, the photosensitive material after processing has no `t'L to be removed.
It has been found that the image stability of photosensitive materials processed under this harsh environment is particularly markedly deteriorated due to the increase in impurities such as n.

However, in the combination of the anti-fading agent according to the present invention and the anionic/dissociatively aggressive water-soluble polymer, the %m image stability did not deteriorate during the regeneration of the above-mentioned standard N solution, and good photographs were obtained. It is worth noting that the gender is improved.

Here, the recycled car Q is 60% or more, preferably 10%
Even in the case of high-level regeneration, the above general formula (1)
In the method of processing the Tomocolor photosensitive material using a next-color-forming GI solution (containing a specific water-soluble polymer), good photographic images can be obtained without causing any adverse effects associated with reproduction (the process of processing the photosensitive material with a specific water-soluble polymer) produces good photographic images without causing any adverse effects associated with reproduction. You can get less)! ! Next.

Here, the reproduction rate Q is means.

The power of the present invention is that the photographic light-sensitive material has color development, bleach-fixing,
It is preferable to perform a water washing treatment (or stabilization treatment).S whitening and fixing may be performed separately rather than in one bath.

The coloring developer used in the present invention contains a known aromatic primary amine active agent.

Preferred f13 is a p-722 fujiami/derivative, representative examples of which are shown below, but not as defined herein.

D-/N, N-diethyl-p-phinyl diamine D-1 co-amino! -Diethylaminotriene D-j Coramino! -(N-edel-N-lacrylaminotontoluene D -4-[N-nibble-N-1β-hydroxyphether)amine]Aniline D-s Cometeru≠-[N-ethel-N(β-hydroxy/ether) aminocoaniline D-6≠-amine-3-mesol-N=ethyl N-Cβ-
(Meta/sulfo/amide)enal]-anili/D-7N-(j-amino-!-noetheraminophenylethyl)methanesulfony/7e-D-r N,N-dimethyl-p-phenylenediami/D- Ta ≠-amino-3-methyl-N-ethel-N-methquinetheraniline D-10tei-amino-3-methyl-N-ethel-N-β
-Etkinedelanili/D-//Guamino-3-methyl-N-ether-N
-β-Futkin ether aniline/Amino-3-methyl-N-edel-N-(β-(
methanesulfonamide) ethylcouaniline (lPII
This is compound D-4).

*a, cn et al.'s 9-7 22-diamine 114 and sulfur #
Dan, salt #! Weir, nitrous II! Salt, 9-) Luenesulfo/
It is better to use salt such as acidic acid. The amount of the aromatic primary amine active agent to be used is about 1 oz per liter of current gII solution.
ty ~ about 20? , F good 2L< is about o, zt^ about 10f
The concentration is

In the practice of this invention, it is preferred to use present S* which is substantially free of benzyl alcohol. Here, the term "substantially free" means that benzyl alcohol aIL preferably has a content of 2 dll or less, more preferably 0.1 d11 or less! Both # and # preferably contain no benzyl alcohol at all.

It is more preferable that the developer 1fjL used in the present invention does not contain any sulfite ions. The sulfite ion not only functions as a preservative for 'fiL's main ingredient, but also has a silver halide dissolving action and reacts with the oxidized herbal medicine to reduce the pigment-forming effect.

Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially no M" means preferably 11 degrees of sulfite ion at or below J, JXlo-" mol/l, most preferably sulfite ion/l.
It does not contain M at all. However, in the present invention,! Excludes a very small amount of sulfite ion used to prevent blackening in processing agent kits in which the developing agent is concentrated before being mixed into a commercial solution.

It is preferable that the developing solution used in the present invention does not substantially contain sulfite ions, but it is further preferable that it does not substantially contain hydroxylamine. Today,
It is believed that while hydroxylamine acts as a preservative in developing solutions, it also acts as a silver block agent, and that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

Here, "not substantially containing hydroxylamine" means that the degree of hydroxylamine is preferably less than r, oxio mol/l, and most preferably does not contain hydroxylamine at all. It is.

The developer included in the present invention includes the hydroxylamine/
or sulfite ion) 4! It is more preferable to contain a preservative.

Here, by adding an organic preservative to the treatment solution of the material, the aromatic primary amine force t -f
j4 Index of all organic compounds that reduce the deterioration rate of herbal medicines. In other words, there is a device 11 for preventing oxidation of the color active ingredient by air, etc. Among the M-like compounds that grow
Hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, human:ysyns,
Shidracytoids, 7x/-lu vesicles 1. α-Hydroxyketo 7
%, α-aminoketo 7, S, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused cyclic amino Ili, etc. It is an effective organic preservative. These et al.
-JOI-tei! No. 6J-co/44t7 No. 63-1
Bow No. 77, 4J-! J! j1, same 13-μ31≠o
4+, AJ-1441-tei, 47-1134t4, 6j-413/31, 4j-/4clsO/
No. 63-1 bow! No. 7, No. 63-Sanko No. 6!6, United States Permit No. 3 and 4! .

No. 503, same co, $P4t, PI3, Tokukaisho! It has not been disclosed in Ko-/uJ020, Special Publication Showat-3ouri No.4, etc.

As other preservatives, each of the akin metal odes described in JP-A No. 7-Hirohiro/≠r and JP-A No. 137-137, salicylic acids described in JP-A No. 11 ojrr, and JP-A Akihiro -31
Alkanolamide described in No. 32, polyethylene imitation class 7 of JP-A No. 6-Tada 3, US patent @j
, 74L4, ! If necessary, aromatic polyhydroxy compounds such as No. 4A'f may be contained. especially alkanolamines, such as triethanolamine,
Preferably, an aromatic polyhydroxy compound is added to a dialkylhydroxylamine such as diethylhuman α-xylamine, a hydrazine conductor or the like.

Among the above-mentioned organic preservatives, hydroxylamine derivatives are particularly preferred, and are compounds represented by the following general formula (A).

General formula (A) (In the formula, L represents a linear or branched alkylene group having 10 or more carbon atoms, preferably carbon number/~!.Specifically, menare/, Preferable examples include ethylene, trimethylene, and propylene. Examples of substituents include carboxy groups, sulfo groups, phosphono groups, phosphinic acid residues, hydroxy groups, alkyl-substituted ammonio groups, Carboxy group, sulfo group, phosphono group, hydroxy group are listed as preferred group 6
Carboxy groups, sulfo groups, phosphono groups, phosphinic acid residues, hydroxy groups, alkyl-substituted amine groups, alkyl-substituted ammonio groups, alkyl-substituted carmemoyl groups, alkyl-substituted Sulfamoyl group t-ff, carboxy group, sulfo group, hydroxy group, phosphono group, alkyl substitution
A preferred group includes a carbamoyl group. −
As L-AQ, carboxyl methyl group, carboxyethyl group, carboxypropy/'3% sulfonidel group, sulfopropyl group, sulfobutyl group, phosphonomethyl group,
Preferred targets include a phosphonoethyl group and a hydroquinether group, and particularly preferred targets include a carboxynemethyl group, a carboxylether group, a sulfoether group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. . R is a hydrogen atom, carbon number/~10
The straight chain I 几 refers to a branched chain optionally substituted alkyl group, and has 1 carbon! /-j is preferred. Substituents include carboxy group, sulfo group, phosphono group, phosphinic acid residue,
Hydroxy group, alkyl-substituted amino group, alkyl-substituted % ammonio group, alkyl-substituted %
Engineered carbamoyl group, alkyl substituted to represent sulfamoyl group.

There may be two or more substituents. R is a hydrogen atom, a carboxymethyl group, CalIF: q diethyl group, carboxinpropyl group, sulfonidel group, sulfopropyl group, sulfobutyl group, sulfonomethyl group, phosphonoether group,
A hydroquine ether group can be cited as a preferred target, and a water bulk atom, a carboxyethyl group, a carboxyethyl group, a sulfonidel group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group can be cited as particularly preferred groups. L and 8 may be connected to form a ring,
) Next, in the specific compound of the present invention, the ligands are limited to n and n, so #'X is not present.

(5)10-N N()12C)i2So3HM-The compound represented by the general formula (A) can be obtained by alkylation reaction (nucleophilic substitution reaction,
Lv can be synthesized by addition reaction and Mannich reaction. West German Special Ff
anica ChimicaActa), P3, (/
(re) tot-ior.

This can be achieved in accordance with the Industrial Design Law, such as

I. The combined use of the above-mentioned hydroxylamine/derivatives and amines is more preferable from the viewpoint of improving the stability of the color developing solution and further improving the stability during continuous processing.

Examples of amines include nine-cyclic amines described in JP-A-63-/KO-13≠θ, and others*! mF@b3-Tough/No. 3 is described in No. 43-11300, and y@ is mentioned.

In the present invention, τ, 3 chloride ions in the color developer, rx
It is preferable that the amount is less than io ni, jxio mol/1. % trap good IL<, ≠XIQ-2~/×10
It is measured in moles/l. Chlorine ion *i is l, JXlo
If the amount is more than A-10 mol/l, the disadvantage is that the development is delayed, and it is not preferable to achieve the object of the present invention, which is rapid development and a maximum of 11 degrees. Also, 3.6X10
If the amount is less than 1 mol/1, it is not favorable for completely preventing fogging.

In the present invention, bromine ions are added to the color developer by J, 0X
70%) k/tq, preferably less than 0x10 mol/1. Ef likes it! ,0X10
~! ×/Q Calculate in mol/l.

If bromine io/11 degrees is /
j, 0X10 Less than 71 moles! Ih stand, Cub'J t-cannot be prevented sufficiently.

Here, chlorine ions and bromine ions are added directly to the developer. % processing, fI is transferred from the light-sensitive material to the developer blue solution during the development process.
! You can take it out.

I for color developer! When added, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lytecum chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, which are preferred. %C) is sodium chloride, potassium chloride. Qb is supplied from a fluorescent brightener added to the developer solution.

As bromine io-10 supplying substances, sodium bromide, potassium bromide, ammonium bromide, lithewum bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among these, the most preferred are potassium bromide and sodium bromide.

When eluted from a light-sensitive material during current processing, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from other than the emulsion.

The color developing gII solution used in the present invention is preferably p
Hri ~/, 2, j 9 good I L<ff5' ~/ /
, 0't'1°, the color developer may also contain other known developer compositions.

In order to maintain the above-mentioned pH, it is preferable to use a buffering agent. As a buffer axe, carbonate, s/a! Dan, Hou II! salt, tetrapho7ate, hydroxy7benzoate, glycyl salt, N,N-dimetergrine salt, leucine salt,
Norloin salt, guanine salt, 31-dihydroxyfuyunirua 22/salt, alanine salt, amine 7N! 1iIl!
Salts such as co-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyamitumethane salt, lysine salt, etc. can be used. Especially Tansan Salt, Su/ll12 Salt, and Shihoku #! The salt, human roxybenzoate, has excellent solubility, pH, and buffering ability in the high pH range of 0 or higher, and when added to the color 3Jl solution, there is no negative impact on photographic performance (fogging, etc.). It is particularly preferable to use these buffering agents because they have the advantages of being free from oxidation and being inexpensive.

Specific examples of these buffers include sodium carbonate,
*lI! Potassium+74, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium/acid, dipotassium/acid, sodium chloride, potassium borate, sodium tetraborate (borax), Potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate) % Potassium 0-hydroxybenzoate, sodium j-sulfohydroxybenzoate (sodium salicylate)
j~s/l/sodium phosaliterate,! Potassium cyanbenzoate (potassium j-sulfosalicylate) in -sulfo λ-hydro may be mentioned. However, unexploited BA is not limited to these compounds.

The amount of the buffer added to the color developing TIl solution is 0.7 mol/
It is preferable that IL<, % o, imol/l-0 is 1 or more.
, II mol/j is particularly preferred.

In addition, various chelating agents can be used in the color developer gII solution as calcium and magnesium precipitation inhibitors and to improve the stability of the color developer solution.

The targets are nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-19metele/
Phosphonic acid, etele/cyamine-N, N, N', N'
- Tetramethylene sulfone rice, transsilohexanediaminetetraacetic acid 1'L cordiaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, edele/diamine orthohydroxyphenylacetic acid, cophosphonobutane/,
l-Hydroxyethylidene-
1,l-diphosphonic acid N.

Examples include N'-bis(co-hydroxybefudine ethylenediamine-N,N'-diacetic acid).

One or more of these chelating agents may be used in combination as necessary.

The amount of these chelating agents to be added may be as long as f'L, which is essential for sequestering metal ionol in the color developing solution.

Meat bite/j 90. /1-IOf purity.

Color development 3I! If necessary, an arbitrary development accelerator may be added to the solution.
Can be added.

As a development accelerator, Tokko, Tokuko Sho 37-iisorr No. 37-jri No. 17, Tokuko 3t-'yrλ6, Tokiko-1
JJfO issue, same da! - Towel No. and U.S. Permit No. J, I
ll, Kohiro No. 7, etc., the people are in charge, 1 ether type monster, Tokukai Sho! Ko≠ri rkota and 30-/j1! p-phenylenediamine type compound, JP-A No. Sho-jo-iJ77λ, JP-Ko-Ko-Ko-JOO-714,
JP-A-54-1jr41ko4 and jko4c3 reference λ
U.S. Patent No. J, 41F4! , F7J issue, same s, tko r, it- issue,
Same #, Ko 30, 7ri No. 4, Same 31λ! 3. Riri No., Special Publication No. 41/-//$3/, U.S. S. No.-94c12
, j$4, same 2. Jri A, No. 924 and J, II
Amine-based compounds described in J$ No. 4, etc.,
itorr issue, Douyu Coco J Co 0/issue, United States~Xu! j,
/ko r, /13 issue, Kosho Ai-tiu3i issue, same≠2
-i3rr3 and U.S. Patent No. J,! ! 2.60/4
Polyalkylene oxide and other
-Phenyl-3-pyranolidone, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added as required. As antifoggants, alkali metal halides/compounds such as sodium chloride, potassium bromide, potassium iodide, and M-type antifoggants can be used. M machine anti-capri agents include benzotriazole, 6-nidropenzimidazole, j-nitroinindazole, j-medelbenzotriazole,! -Nitrobenzotriazole,! -51X heterocyclic compounds such as -chlorobenzotriazole, -theazolylbenzimidazole, cochiazolylmethyl-benzimidazole, indazole, hydroxyazainotridine, adenine 4
[-Can be defeated as a substitute.

The color developing solution applicable to the present invention preferably contains a fluorescent whitening agent. As a fluorescent brightener, ≠, Hiro'-
Diaminorco, -'-disulfostilbene type compounds are preferred. Addition j1 is Q~! t/l, preferably 0. /f
−≠f/l.

Furthermore, various surfactants such as alkyl sulfo/acid, aryl sulfo/acid, aliphatic Cal 1721 aromatic carboxylic acid, etc. may be added as necessary.

The processing temperature of the color developing solution applied to the present invention is xo~s
o @C1 or j O-4cO°C terror. Processing time is 0 seconds! Minutes, good IL < is 30 seconds to - minutes.

Although it is preferable that the amount of replenishment is small, -Q~AOOd per M optical material/m is appropriate, and preferably jO~JO
It is Od. More preferably 6o, 114-λ00xl
, most preferably POd~/JOd'''C.

Next, a desilvering process that can be applied to the present invention will be explained.

What kind of processes does the desilvering process include - a bleaching process, a fixing process, a fixing process - a bleach-fixing process, a bleaching process - a bleach-fixing process, a bleach-fixing process, etc.? May be used.

In the present invention, the desilvering process 8i is performed immediately after the color development process, and the overflow liquid of the desilvering process liquid is recycled and used.

For recycling and use, supplementing the processing aha components consumed during processing of the over-70-solution, and pre-bath processing g carried by the photosensitive material.
In order to maintain the performance of the processing liquid, such as the next adjustment to completely eliminate the influence of acid components, a regenerating agent is added and reused.

Normally, a certain amount of replenisher is supplied to the 1A photosensitive material in order to optimally develop the performance of the photosensitive material for the amount of processing per unit area. Then, the over was 70-1.
If FI is used with analytical methods used by woodcutter (for example, potentiometric titration, high-performance liquid chromatography, atomic absorption spectrometry, etc.), it will be possible to obtain the same performance as a replenisher to optimally express the performance of the photosensitive material. can be made at-reproducible.

In this way, over 70-liquid* can be used as a regenerating agent.
The number of minutes per volume (chemical) and its amount, p) f, etc. can be determined.

The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below.

Any bleaching agent can be used as a bleaching agent in the bleaching solution or bleach-fixing solution, but especially iron(m) Ma! Complex salts (e.g. ethylenediaminetetraacetic acid,
Aminopolycarboxylic acids such as diethylenetriamine, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid, and VM phosphonic acid) or f-organisms such as citric acid, tartaric acid, and malic acid; persulfates; peroxides; Hydrogen and the like are preferred.

Among these, organic complex salts of iron (I[l) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution;
'Aminopolycarboxylic acids, aminopolyposboxylic acids, or organic phosphonic acids or their salts that are useful for forming UtW salts include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, Acids such as propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, meteliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, etc. can be suppressed. These compounds may be sodium, potassium, thium or ammonium salts; among these compounds are iron ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodiacetic acid; (I[[)tW salt is preferred because it has a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and diferrous phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolybosphonic acid, or phosphonocarboxylic acid.
Aminopolycarboxylic acid iron complexes are preferred among iron complexes, which may be used in excess to form iron ion salts, and the amount added is 0.01 to 1.0 mol/2, preferably 0.05 ~0.50 mol/j! It is.

The bleaching solution, bleaching solution ffL and/or their pre-bath may include:
Seed compounds can be used as purity promoters1
For example, U.S. Pat.
SS3O Publication, Research Disclosure No. 171
No. 29 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
No. 506, Japanese Patent Publication No. 52-2 (1832, No. 53-32)
Thiourea compounds described in No. 735, US Pat. No. 3,706,561, and halides such as iodine and bromide ions are preferred because they are convenient for bleaching blades.

In addition, bromides (e.g., potassium bromide, sodium bromide,
ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodide 1
Rehalogenating agents such as 7I (eg, ammonium iodide) can be included. If necessary, use borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. with pH buffering capacity.
More than one type of inorganic acid, organic acid, alkali metal or ammonium salt thereof, or a corrosion preventive agent such as ammonium TA acid or guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution can be any of the known fixing agents, namely thiosulfates such as sodium thiograte and ammonium periosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; These are water-soluble silver halide dissolving agents such as glycolic acid, thioether compounds such as 36-cythia-1,8-octanediol, and thiourea, and these can be used alone or in combination of two or more.

In addition, a special bleach-fix solution made of a combination of a fixing agent described in JP-A-55-155354 and a large amount of potassium iodide and a halide may also be used.In the present invention, thiosulfuric acid The amount of fixing agent per 12 salts, particularly ammonium periosulfate salts, is preferably used.
Preferably 0.3 to 2 mol, more preferably 0.5 to 1 mol
．． It is in the range of 0 mol. Bleach-fix or fixer pi (
The range is preferably 3 to 10, and particularly preferably 5 to 9.

In addition, the clean fixer may contain various other fluorescent brighteners, antifoaming agents, surfactants, and solvents such as polyvinylpyrrolidone and methanol.

Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.).

These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
The content is preferably 0.05 mol/l, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary.

After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed.

The amount of water used in the washing process varies widely depending on the characteristics of the optical material (for example, depending on the materials used such as couplers), the purpose, 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 to . Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Modern Picture and Television Engineers.
nalof the 5ociety of Moti
on Picture and T@1evi-sio
n Engineers) Volume 64, p, 248-25
3 (May 1955 issue).

Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, to 0.51 to 12 or less per bottle of photosensitive material, and the effect of the present invention is remarkable. The increased residence time causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. As a solution to such problems, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Also, JP-A-57-85
Chlorine disinfectants such as isothiazolone compounds and thiabendazole compounds described in No. 42, chlorinated sodium incyanurate described in No. 61-120145, JP-A-61-2
Benzotriazole, copper ions, etc. described in No. 67761, Hiroshi Horiguchi, "Chemistry of antibacterial and anti-mildew J (1986), Sankyo Publishing, Hygiene Technology Metals, "Extermination of microorganisms, sterilization, anti-mildew technology" (1982) Industrial technology It is also possible to use the fungicides described in Akebono's Dictionary of Antibacterial and Antifungal Agents J (1986) of the Japanese Society of Antibacterial and Antifungal Research.

Further, in the washing water, a surfactant may be used as a draining agent, and a chelate law such as EDTA may be used as a water softener.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound such as formalin, a buffer to adjust the membrane pH through dye stabilization, or an ammonium compound. . Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners may also be added.6 In the processing of the photosensitive material of the present invention, if stabilization is performed directly without going through a water washing step, JP-A-57-
No. 8543, No. 58-14834, No. 60-2203
All known methods described in No. 45 and the like can be used.

In addition, it is also preferable to use a chelate such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetemethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing solution is also used as a washing solution or stabilizing solution used after desilvering treatment.

The preferred pH of the water washing step or stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is between 15 and 45 degrees.
C The period of 6 hours, preferably 20 to 40°C, can be set arbitrarily, but a shorter time is desirable from the standpoint of reducing processing time, preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 30 seconds. It is. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. Or photosensitive material r4 inches (12 or less, preferably 500 or less per unit).Furthermore, replenishment may be carried out continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to reduce the amount of waste liquid by using a multi-stage countercurrent system to allow the overflow of the washing water to flow into the bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with smi.

The color photographic window optical material of the present invention is constituted by coating on a support at least one layer each of a blue S-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer. I can do it. In general color photographic paper, the layers are usually coated on the support in the order listed above, but they may be coated in a different order. It can be used in place of at least one of the above-mentioned papillary layers. These photosensitive emulsion layers contain silver halide emulsions that are sensitive to each wavelength range, and pigments that are complementary colors to the emitted light - yellow for blue, magenta for green, and cyan for red. −
By containing a so-called color coupler that forms a color, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

As the silver halide emulsion used in the present invention, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide 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, even if the halogen composition of the emulsion differs between grains. Although they may be equal, if an emulsion having an equal halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) [-layer or multiple layers] Particles with a so-called laminated structure in which the halogen composition is different, or
Particles with a structure that has parts with different halogen compositions in a non-layered manner inside or on the particle surface (if on the particle surface, parts with different compositions are joined on the edge, corner, or surface of the particle) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is more advantageous to use one of the latter two than grains with a uniform structure, and it is also preferable from the viewpoint of pressure resistance, and silver halide grains having the above structure are preferred. In this case, the boundary between parts that differ in halogen composition is
The boundaries may be clear, or may be unclear due to the formation of mixed crystals due to compositional differences, or may have continuous structural changes.

Regarding the halogen composition of these silver chlorobromide emulsions, any li bromide/silver chloride ratio can be used. Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used.

Furthermore, so-called high silver chloride emulsions having a high silver chloride content are preferably used for S optical materials that have been subjected to rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more.

In such a high silver chloride emulsion, it is preferable to have a structure in which the silver bromide localized layer is formed inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above.The halogen composition of the localized layer is as follows. The silver bromide content is small (preferably 10 mol%, more preferably more than 20 mol%), and these localized layers are formed inside the grain, at the edges, corners, or on the surface of the grain. However, one preferred example is one in which epitaxial 6-A is applied to a part of the corner of the particle.

On the other hand, in order to minimize the 5 degree drop when the optical material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, a uniform structure with a small distribution of halogen composition within the grains is used. The use of particles is also preferably carried out.

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In this case, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.14 to 2-.

In addition, their particle size distribution has a coefficient of variation ('rX'5 deviation of particle size divided by average particle size) of 20
% or less, desirably 15% or less, so-called monodisperse emulsions are preferred. In this case, the above-mentioned monodisperse emulsions may be blended in the same layer for the purpose of obtaining a wide latitude.
Multilayer coating is also preferably carried out.

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar) Those that have crystal shapes, those that grow irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, one that grows a combination of these can be used. In addition, it may be made of a mixture of particles that grow various crystal forms.In the present invention, among these particles, particles having the above-mentioned regular crystal form account for at least 50%, preferably at least 70%, and more preferably at least 70%. The content is preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the emulsion grain formation or physical formation process.

Examples of compounds used include dominium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies widely depending on the purpose, but is preferably 101 to 104 moles relative to silver halide.

The silver halide emulsion used in the present invention is usually chemically enhanced S
and spectral sensitization.

Regarding the chemical enhancement method, sulfur enhancement typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction enhancement can be used alone or in combination. Regarding compounds used for chemical exacerbation, please refer to the lower right corner of page 18 of the specification of JP-A No. 62-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral enhancement is performed for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the optical material of the present invention. It is preferable to add a dye that absorbs light - a spectral-enhancing S dye. Examples of the spectral-enhancing dye used in this case include He, by F. M. Hara+er.
terocyclic compounds-Cyan
ine dies and relat@d comp
ounds (John Wiley & 5ons (
(New York, London), 1964). As specific examples of the compounds, those described in the above-mentioned Japanese Unexamined Patent Publication No. 62-215272, page 22, upper right column to page 38, are preferably used.

The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. These are commonly referred to as photo stabilizers. As specific examples of these compounds, those described in JP-A-Sho (i2-215272), pages 391i to 72 are preferably used.

The emulsion used in the present invention may be of either the so-called surface-image type papule, in which the accumulated image is mainly formed on the grain surface, or the so-called inner layer-image type, in which the accumulated image is mainly formed inside the grain. It's okay to meet with something.

When the present invention is applied to color S light material, cough collar 5
Optical materials usually include yellow couplers, magenta couplers, and cyan couplers that produce yellow, magenta, and cyan colors, respectively, when coupled with aromatic amine color-forming compounds (oxidized products of straw).

Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention have the following general formulas (CN, (C-TI), (M-[), (M-!I)
and (Y).

General formula (C-1) H -Female mosquito (C-n) General formula (Y) 0 ■ One female mosquito CM-I) General formula (M-n) X! 1 Zc=Zb In general formulas (C-I) and (C-II), R,,
R, and R4 represent a monosubstituted or unsubstituted aliphatic, aromatic, or heterocyclic group; R3, R1, and R1 represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group; R1 is Yl may represent a group of nonmetallic atoms forming a 5- or 6-membered M-containing ring together with R2;
, Y2 represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent, and n represents O or 1.

RS in the general formula (C-I[) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadenyl star, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, Phenylthiomethyl group, phenylthiomethyl group, butanamidomethyl group, methoxymethyl group, etc. can be excluded.

Preferred examples of the cyan coupler represented by the claw type (CL) or ('Cf[) are as follows.

In general formula (C'-I), R1 is preferably an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, More preferably, it is an aryl group substituted with a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

-i When R3 and R2 do not form a ring in formula (C-1), R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R1 is preferably a hydrogen atom.

In the general formula (C-n), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy alkyl group.

In the general formula (C-n), R1 preferably has 2 to 1 carbon atoms.
5 alkyl group and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

- In the female mosquito (C-If), R2 is an alkyl group having 2 to 15 carbon atoms. More preferably, the number of carbon atoms is 2 to 4.
Particularly preferred is an alkyl group.

- In the female mosquito (C-I [), preferably 7 is an elementary atom,
A halogen atom, with chlorine and fluorine atoms being particularly preferred. Yl and Yz, which are preferred in (C-1) and (C=n), are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, respectively. group, a sulfonamide group.

In one female mosquito CM-I), R7 and R9 represent an aryl group, R1 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a leaving group.

Aryl group (preferably phenyl group) of R1 and R1
The substituents allowed for are the same as the substituents allowed for the substituent R+, and when there are two or more substituents, they may be the same or different, tllll is preferably a hydrogen atom, It is an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom.

Preferred Y is of the type that leaves off with either sulfur, oxygen or M atoms, for example as described in US Pat. No. 4.3.
51.897 and International Publication W088104795 are preferred for poetry.

In the general formula (M-It), Le is a hydrogen atom or 1
Za, which represents a substituent, Y4 represents a hydrogen atom or a leaving group, and a halogen atom or an arylthio group is particularly preferred;
Zb and Zc are methine, substituted methine 1, N- or -1
1) Represents I-, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

When the Zb-Zc bond is a carbon-carbon double bond, including when it is part of an aromatic ring, when it forms a dimer or more multimer with R1゜ or Y4, and when Za, zb (1) When Zc is a substituted methine, it includes the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (M-n), imidazo(L,2- b) Pyrazole necks are preferred, pyrazolo (1,5
-b)(1,2,4) triazoles are preferred for frames.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226. It is preferable to use the alkoxy 7NE or aryloxy group-based couplers described in No. 849 and No. 294.785 having t% of alkoxy 7NE or aryloxy groups at the 1-position.

-ff In the formula (Y), B□□ is a no-rogen atom,
Alcoquine group, 19 trifluoromethyl groups, 6 aryl groups in total, R1□ is a hydrogen atom, 19 halogen atoms are Alcoquine Foundation. A is -N)icOR□1, -N)iso
-Bon , -8O□N)1Bon□3. -COO 0.
, -SO□N-R Engineering, ni Omotesato.

"14 However, R13 and h□4 are respectively n alkyl, aryl, or acyl groups, and Y5 is a leaving group. 几1□
and "13%" as a substituent of 14 is the same as the t'Lfc substituent allowed for R, leaving group Y, preferably an oxygen atom% L< is any nitrogen atom. Particularly preferred is a type with a small amount of t, which is separated by a large amount of nitrogen.

The above female mosquitoes (C-1) to (Y) extend the length of the coupler,
In the silver halide emulsion layer constituting photosensitive R1, there is usually 0.1 l) per mole of silver halide. /-/.

0 mol, good IL (0.1 to 0.! mol) is included in feces.

In the present invention, after adding the coupler to the TG source, a known technique can be applied. Normally, oil droplet dispersion known as oil protection method =
After dissolving in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. In a coupler solution containing a surfactant, trap water or gelatin water f
A dispersion of oil droplets in water may be obtained by adding g and phase inversion.

Primary alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low boiling point organic solvent #Et is removed by distillation, noodle washing or ultrafiltration, and then mixed with a photographic emulsion.

As a dispersion medium for such a coupler, a dielectric wire (2!@C
)2~2o, refractive index (λr@c)i.

It is preferable to use all of the high boiling point organic solvent of j-/, 7 and the water-insoluble polymer compound of 71m.

As a high boiling point organic solvent, the following general formula (A) ~
In (E), the high boiling point organic solvents that are present in the mixture will be removed.

General formula (A)? W, -0-P=0 General formula CD) wl-coo-w2 General formula (C) General formula CD) General formula (E) W -0-W2 (In the formula, W□, W2 and Wsix) Substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group kW, W4 is W□, 0
W1x or S-W, where n is 7 or an IO integer, and when n is 2 or more, W4 are the same and t different from each other, and - in a female mosquito (E), W□ and (W2 may form m rings) 6 The high boiling point organic solvent that can be used in the invention is - female mosquito (A)
% melting point #t o 'C
The following compounds are immiscible with water and have a boiling point of 0@C or higher and can be used as coupler OaS media. High boiling point M
The melting point of the bath medium is preferably 1 or less than ro"c. The boiling point of the high boiling point organic solvent is preferably 110@C or more,
Meng 9 is preferably 70"C or higher.

Regarding these high-boiling point 111fi medium O bonds, please refer to No. 1j7 of the publication specification of JP-A No. 6, 1987/727, lower right 1.
- It is written in the upper right column of the room.

Also, this nG) o coupler c, +, i + 6 boiling point w
In the presence of I1m medium and in the absence of txh, the loader pull latex polymer (see US Pat.
No.) and impregnated with water-insoluble and armature #! # for medium-soluble polymers! It can be emulsified and dispersed in an aqueous colloid solution.

Preferably, the homopolymer 19 copolymer described in International Publication No. WOrr7oo7co No. 3 Specification, pages 1 to 30 is #
It is preferable to use an acrylamide-based polymer with no acrylamide-based polymer on the bone in terms of color image stabilization and the like.

Hydroquinone derivatives, amino 7-E/- as sensitizers, materials, and color antifoggants made using unexploded HAt-
Kill conductors, gallic IlliI conductors, ascorbic acid derivatives, etc. may be used.

The unexploded IIAOIIA optical material has the general formula (1) of the present invention.
There are 111 different kinds of omniscient compounds! !
.

Can be used in combination with inhibitors. That is, V! for cyan, magenta and/or yellow ms. lI anti-fading 41 includes hydroquino 7, 6-human'loki 7 chromans,! -Hydroxykumara 21jt spirochromans, p
-Alkoxyphenols, bisphenols*t-centered hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and the phenolic hydroxyl groups of these compounds are silylated and alkylated. Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel phase and (bis-N,N-dialkyldithiocarbamado)nickel complexes can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are U.S. Patent No. 2,350.290,
No. 2,418,613, No. 2,700.453, No. 2,701.197. No. 2,728,65
No. 9, No. 2,732.300, No. 2.735,7
No. 65, No. 3,982.944, No. 4.430.
No. 425, British Patent No. 1.363.921, US Patent No. 2.710. E101, U.S. Patent No. 2,816.028, etc., 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are disclosed in U.S. Patent No. 3,432,
No. 300, No. 3.573,050, No. 3,574
, No. 627, No. 3.698゜909, No. 3,76
4.337, JP-A-52-152225, etc., and spiroindanes are described in U.S. Patent No. 4.360.5B9,
P-alkoxyphenols are described in U.S. Patent No. 2.735.
No. 765, British Patent No. 2,066.975, JP-A No. 5
No. 9-10539, Special Publication No. 57-19765, etc.
Hindered phenol lamp is U.S. Patent No. 3,700,45
No. 5, JP-A No. 52-72224, U.S. Patent No. 4, 22
8, 235, and Japanese Patent Publication No. 52-6623, gallic acid derivatives, methylenedioxybenzenes, and amine phenols are disclosed in U.S. Patent No. 3,457,079, respectively.
No. 4,332,886, Japanese Patent Publication No. 56-21144, etc., and the hindered amine face described in U.S. Patent No. 3.336.
No. 135, No. 4.268.593, British Patent No. 1.
326°889, same No. 1,354.313, same No. 1
．． 410.846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 58-114036, Japanese Patent Publication No. 59-53846, Japanese Patent Publication No. 59-78344, etc.;
No. 050,938, British Patent No. 4.241155, British Patent No. 2.027,731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with a coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to light exposure, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,794)
), 4-thiazolidone compound! ! ! 71(
For example, U.S. Patent Nos. 3,314,794 and 3352
．． 681), benzophenone compounds (
For example, those described in JP-A No. 46-2784), cinnamate ester compounds (for example, those described in U.S. Pat. No. 3,705°80)
No. 5, U.S. Pat. No. 3,707,395), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., U.S. Pat. No. 3,700. 455) can be used. UV-absorbing couplers (e.g. α-
A naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may also be used.

These ultraviolet absorbers may be mordanted in specific layers.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition, it is particularly preferable to use the following compounds together with the couplers described above, particularly in combination with pyrazoloazole couplers.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferable compound (F) has a second-order reaction rate constant kg (in trioctyl phosphate at 80'C) with P-anisidine of 1.02/mol·sec to 1×10−
It is a compound that reacts in the range of 'l/■ol-sec.

Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

If 2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k: is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

A more preferable compound (F) can be represented by the following general formula (Fl) or (FI[).

General formula (Fl) R, -(A), -X General formula (Fn) R,7C禦Y In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group, and n is Represents 1 or 0.

A represents a group that reacts with an aromatic amine developer to form a chemical bond, χ represents a group that reacts with an aromatic amine developer and leaves, B represents a hydrogen atom, an aliphatic group, an aromatic group group, heterocyclic group, acyl group, or sulfonyl group,
Y represents a group that promotes the addition of an aromatic amine developing agent to the compound of general formula (Fn), where R+ and X, Y and R2 or B are bonded to each other to form a cyclic structure. It's okay.

Among the methods of chemically bonding with residual aromatic amine-based developer, what are the typical methods? These are exchange reactions and addition reactions.

For specific examples of compounds represented by general formulas (FI) and (Fn), see JP-A-63-158545 and JP-A-62-2.
83338, European Patent Publication No. 298321, European Patent Publication No. 277
Those described in specifications such as No. 589 are preferred.

On the other hand, more preferable compounds (G) that chemically bond with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound are listed below. It can be represented by [).

General formula (]) In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and Z is a nucleophilic group or a group that decomposes in a photosensitive material to release a photophilic group. Compounds represented by -infection (CI) are those in which Z is Pearson's nucleophilic IICH (CI)
Direct (R,G, Psarson, et al., J
, Am.

ChelIl, Sac,, 90.319 (196
8)) is preferably a group having 5 or more, or a group tffi-formed from it.

- For specific examples of compounds represented by CI, see European Patent Publication No. 255722, JP-A-62-1430.
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-214681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589.

The irradiance material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol. Dyes include hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the miko material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the gelatin manufacturing method can be found in The Macromolecular Chemistry of Gelatin, written by Arthur Weiss. Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene terephthalate, which are usually used in photographic photosensitive materials, and reflective supports can be used. Use is more preferred.

The "reflective support" used in the present invention is one that has high reflectivity and makes the dye image formed in the silver halide emulsion layer clear. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. 6 For example, baryta paper, polyethylene coated paper, polypropylene synthetic paper, light support with a reflective layer or a reflective material, such as glass plate, polyester such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate. film, polyamide film, polycarbonate film,
Examples include polystyrene film and vinyl chloride resin.

As other reflective supports, supports having a specular reflective or second type diffuse reflective metal surface can be used. The gold rII surface preferably has a spectral reflectance of 0.5 or more in the visible wavelength range, and it is also preferable to roughen the metal surface or make it diffusely reflective by using metal powder. Examples of such metals include aluminum, Tin, Stainless steel, magnesium, or an alloy thereof may be used, and the surface may be a metal plate, metal foil, or metal TRN surface obtained by rolling, gluing, plating, or the like.

Among these, it is preferable to obtain the metal by depositing the metal on another substrate.It is preferable to provide a layer of water-resistant resin, especially a thermoplastic resin, on the metal surface. It is preferable to provide an antistatic layer on the opposite side of the support.For details of such a support, see, for example, JP-A No. 61-210.
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc.

These supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjoining unit areas and dividing the area of fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%) (Rz). The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/R of the m1ss difference S of R4 to the average value (R) of R4. The number of target unit areas (n) is preferably 6 or more, and therefore the coefficient of variation s/R can be determined by s/R.

In the present invention, the variation coefficient of the occupied area ratio (%) of the pigment fine particles is preferably 0.1S or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles is practically uniform. ” can be said.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these embodiments.

Example 1 A multilayer color paper having the layer structure shown below was prepared on a paper support whose surface had been laminated with polyethylene and whose surface had been subjected to corona discharge treatment. The coating solution was prepared as follows.

Preparation of first layer coating solution: yellow coupler (ExYl≦o, og and anti-fading agent (Cpd-/)) 20. Ofi and ethyl acetate/jOc
c and solvent (Snlv-J) J, OCC and solvent (So
1 v -1) 4,0 Oct- was added and dissolved, and this solution was diluted with diimpa pyrunaphthalene sulfonate/10-containing sodium sulfonate and sodium dodecylbenzene sulfonate.
Gelatin aqueous solution 41! After adding it to Occ, it was dispersed with an ultrasonic homogenizer, and the resulting dispersion was mixed and dissolved in a silver chlorobromide emulsion (0.7 mol of silver bromide) 4A201ifC containing the following blue-sensitive sensitizing dye. A first layer coating solution was prepared.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer! /, j
-k”s(vinylsulfonyl)ethane was used.

The following spectral sensitizing dyes were used throughout each layer.

Blue-sensitive emulsion layer; anhite a-r, t'-diku c1cI-
j,j'-disulfoethylthiacyanine humaniokid green-sensitive emulsion layer: anhydro-2-ethyl-! ,! '-diphenyl-J, J'-disulfoethyl oxacarbocyanine hydroxide red-sensitive emulsion layer; J, J'-diethyl-! -methoxytheta, l/-neo-intithiazidylupocyanine iodide The following compounds were also used as stabilizers for each emulsion layer.

9. Use the following as an irradiation-preventing dye.

[3-Karzexy! -human σ xy-$-(j-(3-
carboquine-j-okine-/-(co,!-bisulfonatophenyl)-2-pyrazoline-hiro-ylidene)-/-propenyl)-/-pyrazolyl]benzene-2. ! -Disulfonate-disodium salt N,N'-(4', r-dihythm a+cy,/.

Geokin-J,? -Disulfonatoanthracene-/!
-diyl 2bis(aminomethanesulfonate 2-tetrasodium salt [3-cya/-!-hydroxy-41-(j-(3-cyano-j-okine-7-(sulfonate phenyl))
-copyrazoline-≠-yritene)-l-be/tanyl)
-7-pyrazolyl]benzene-Hiro-sulfonate sodium salt (layer structure) The composition of each layer is shown below. The number represents the coating amount (g/m2). The silver halide emulsion represents the coated amount in terms of the weight.

-th layer (blue-sensitive layer) gelatin/rg Silver chlorobromide emulsion mentioned above (silver bromide 0.7 mol) o, ag yellow coupler (EXY) o, 19 fading fat fixing agent (Cpd-/
) 0. λ9 color mixing inhibitor (Cpd-co)
0. J9 solvent (8o1v-J) 0. OJi
Solvent (8o1v-see) o-otg second layer (
Color mixing prevention layer gelatin 0.19 Color mixing prevention agent (
Cpd-Co) 0. Ojp solvent (8o lv-/
) 0, Oj9 solvent (So Iv-λ)
Q, θ/rjl Third layer (green-sensitive layer) Gelachi: y /, jp Silver chlorobromide emulsion (Silver bromide /, j mole) 0.3-g Magenta coupler (ExM) 0. Core solvent (Solv-/)
0.07 Solvent (Solv-J)
0.20 Fourth layer (color mixing prevention layer) Gelatin/Huff 0 Color mixing prevention agent (cpct-2) Q, θ6! Ultraviolet absorber (UV-t) o, us Ultraviolet absorber (UV
-2) 0.23 solvent (Solv-/)
0.0! Solvent (8o1mer2) 0.0
2 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion described above (A g B mol - 1 cube, average grain size 0.1 μm) -/) Cyan coupler (ExC-2) Anti-fading agent (Cpd-/) Solvent (Solv-i) Solvent (Solv J) Color accelerator (Cpd-j) Sixth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber ( UV-/) Ultraviolet absorber (UV-2) Solvent (8o1v/) Solvent (Solv-Cot 7th layer (protective layer) Gelatin (ExY) Yellow coupler 0.2 ≦ 0, / CoQ, Co O o, 1t OlQri0,/! 0 .70 0 + 26 0.07 0 + 30 0.02 1.07 (Ex M ) Magenta coupler α (ExC-/) Cyan coupler LtLs l'il 1 (Cpd-/) Fading Inhibitor 10GHz-CH+.

C0NHC4H#) Average molecular weight to, oo.

(Cpd-J) 11 color inhibitors! -J6rt-Octylnohydroquinone (Cpd-3) Color accelerator p-(p-toluenesulfonamide) 7enyludodecay (Solv-/) @ medium di(coethylhexyl) phthalate (8o 1v-2) solvent dibutyl 7 tallate (8o1v-J) solvent di(i-nonyl) 7 tallate (8o1v-4') full medium N, N-diethylcarbonamide methoxyco, dark-t-amylbenzene (UV-/) ultraviolet absorber Co-(co-hydroquine-J,j-di-tert-amylphenyl)benzotriazole (UV-J) ultraviolet absorber Co-(co-hydroquine-3.!-di-tert-zotylphenyl)benzotriazole Sample obtained as above -1O7.

Next, try @io2 and later t- As shown in Table 1, the third layer (
Samples were prepared by adding various anti-fading agents, including a compound represented by the general formula (13) of the present invention, to the green-sensitive layer).

The obtained sample was cut and processed, a green filter was attached to the front of the wedge to give it a full rattan glow, and the treatment described below was carried out. Incidentally, the samples were subjected to gradation exposure for centimetry after FLR was cumulatively replenished in an amount three times the volume of the mother solution of the color developer. Continuous processing (running 7 processing) until the cumulative replenishment amount reached 3 times the amount f- was carried out by applying imagewise light to sample 10/.

The following performance was evaluated for the obtained treated sample.

(1) Concentration difference (ΔDY) between the lowest concentration portions of samples stored under the conditions of ftO'C, 7O-RH for several months after continuous stain treatment and measured with blue light at the end of the test and before the start of the test.

(2) Light fastness of magenta color images The continuously processed samples were arranged outdoors under a glass surface facing south, exposed to sunlight for 3 weeks, and then their concentrations were measured.The concentrations λ and O before the start of the test were The density (D) at the given exposure amount and at the same exposure amount after the end of the test was read, and color image remaining 0 = (D/2.0) x 100 was calculated.

The larger the value, the higher the robustness.

(3) Stability of continuous processing of magenta color images The minimum #Af difference (ΔDmin) and the maximum density difference (ΔDmax) a of magenta color images before and after the start of continuous processing are shown in absolute values.

The results obtained are summarized in Table 1.

Treatment process temperature! Image Refill amount 1 Tank capacity color development ≠06C≠! Second Ta081 4L
l Bleach fixing 30~J4'C4tj seconds co/jal
Hiro! Stable ■ 30~37°C 20 seconds - Stable ■ 30~37°C 20 seconds - Stable ■ 3Q~3
7°C 20 seconds 36 Hirod 21 drying 7O-4j'
The amount of replenishment per CtO second photosensitive material/m2 (3-tank countercurrent system from stable ■ to ■) was used. The composition of each processing solution μ is as follows.

Color wound liquid Tank liquid Neji liquid water
r00HI! 00w1 Polymer of the present invention (see Table 1) o, zg o, tg ethylene fujimineteta, san g ta, hirog laphosphonic acid diethylene triamy y /, 29 /, 2f
i Pentaacetic acid/-Hydroxyethyl o, tg o, t! 9
Den-/,/-diphosphonic acid triethanolamine sodium chloride potassium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-sulfonate-aminoaniline sulfate N,N-diethylhydrogen a Xylamine sodium sulfite fluorescent whitening agent (Sumitomo Chemical WHITEX-←) Add water / 000MlpH<21
@C) 10. DO bleach-fix solution (same as tank solution and auxiliary solution) Water IL
OO114 Ammonium thiosulfate (yoo971) 00
0m 1/, 00 o, ig o, kogi, ago, koI 0, 0jvnolO, 01rno1 tz, og iz, og r, θI 0.0ijg 8 g discussion g z, og iz, og ν Sodium sulfite / 7 iEthylenediaminetetraacetic acid iron (1) Ammonium 11 9 Ethylenediamine/tetraacetic acid disodium! 9 glacial acetic acid
Add 2g water
1ooo νpH (koj'c) r,
Hiro 0 stable solution (tank liquid and auxiliary liquid have the same laformalin (37 t) 0./g formalin-(j! Yabu adduct 0.7 ij-chlorocomethyl-￥- intiazolin-3-one 0.02 flλ -Methyl-zhen-inthiazolin 3-one o, oig sulfate steel
□, 9 oz ammonia water (2
1%) Add 2.0g water
1000 mph (Jj'C)
*, 0 Comparative compound (A-/) Comparative compound (A-con7.7'-dihydroxy-p,4t,l,4t'-tetramethylco,2'-subialoma/From the results shown in Table 1, A common cold treatment that satisfies the constituent requirements of the present invention is to use a compound represented by the general formula (I) in a color photosensitive material and process it with a processing solution in which a water-soluble polymer having an anionic group tV is used as a color developer fA27D. , clearly suppresses the occurrence of yellow stain, maintains the light fastness of magenta color images, and improves the photographic performance (Dm) of magenta color images during continuous processing.
It can be seen that excellent performance is exhibited with small fluctuations in ia and Dmax). (Mu/J-/j, Muko l~ko-) Example 2 Based on sample 10/ prepared in Example 1, each layer including the third layer (green-sensing layer) was coated as shown in Table 2. All samples were prepared by adding the compound represented by the general formula (1) of the present invention.

The obtained sample was subjected to all the same treatments as in Example 1, and its performance was evaluated.

In addition, for the use of the water-soluble polymer of the present invention in a color developing solution,
The experiment was carried out with Pt set at θ and j9/l.

The results are summarized in Table 2.

A-j (tic 4 H9 A-μ -j From the results in Table 2, the compound represented by the general formula (1) of the present invention is used in a color photosensitive material, and.

By adding the water-soluble polymer having an anionic group of the present invention to a color developing solution and processing it, both the light fastness of yellow stain and magenta color images are improved, and
Furthermore, photographic performance in continuous processing (Dmin and Dm
ax) can also be improved to enable stable continuous processing.

Furthermore, if the amount added to the compound represented by female mosquito (1) is small, the above effect will be small, and if it is added in a large amount, the effect will certainly be large, but it can be seen that the effect almost reaches its maximum in terms of photographic performance. . Note that if the amount added is large, the maximum density 1f (Dmax) of the magenta color image decreases.
Observed from u.9.

Furthermore, it is preferable that the compound represented by the general formula (1) of the present invention be used in the green sensitive layer and its adjacent layer. From or sample ko/kotoko 13
It can be inferred from.

Example 3 Using sample 101 prepared in Example 1 and sample 14 prepared in Example 2, the water-soluble polymer of the present invention used in the color developer in the process described in Example 1 is shown in Table 3. After continuous treatment with Sample 10/10 according to the same method (described in Example 1) with the modifications as shown, performance evaluation was performed.

The obtained results are summarized in Table 3.

Table 3 shows that when the water-soluble polymer containing the anionic group of the present invention is used in a color developer and the color light-sensitive material containing the general formula (I) tl- of the present invention is processed, yellow stain , which exhibit surprising effects in significantly improving the lightfastness of the 1 zenta color cast and the variation in photographic performance in successive processing.

Example 4 Sample 10/, -7λ, prepared in Example 1 and Example 2
Kol! and λ/6, and the treatment temperature and treatment time of the treatment described in Example 1 were changed as shown below. At this time, the water-soluble polymer of the present invention was added to the color developer as shown in Table 1. Further, performance evaluation was performed according to the method described in Example 1.

The obtained results are summarized in the following section.

Processing process Color development bleach fixing stable ■ Stable ■ Stable ■ Drying processing temperature≠l'''C 3!0C jO'c JO'C: O0C ri0'C Processing time 30 seconds 30 seconds 10 seconds io seconds 10 seconds 30 seconds From the results in Table 1, it can be seen that when the color photosensitive compound containing all the compounds represented by the general formula (1) of the present invention is treated with the color developing solution containing the water-soluble polymer of the present invention, the results described in Example 1 Even if all steps of color development, mill fixation, stabilization, and drying are carried out quickly, yellow stain and magenta color fastness and processing stability in continuous processing are both superior and improved. It is clear that this occurs.

Example 5 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

72.1 g of yellow coupler (ExY), 4 c of color image stabilizer (Cpd-/), all and color image stabilizer (Cp
d-7) 27.2 generations of ethyl vinegar and solvent (
Solv-/)r and λI were added and dissolved, and this ff1. H
'to 10% sodium dodecylbenzenesulfonate ra
10% gelatin aqueous solution containing ce/r! It was emulsified and dispersed in a flash. On the other hand, a solid silver bromide emulsion (cubic 5 average grain size o, r
A 3-near mixture of rμm and 0.70Am (
Silver molar ratio 9 Coefficient of variation of particle size distribution Ho, or and 0
, / 0゜ Each emulsion contains silver bromide Q, λ mol (localized on the grain surface), and the following blue-sensitive sensitizing dye (contained locally on the surface of the grain) is 5 co, OX for the large size emulsion per 7 mol of the blue-sensitive sensitizing dye shown below. /Q
After adding 10@-4 moles of .lambda.-jrX to the small-sized emulsion VC, sulfur sensitization was performed. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the ms-th fabric solution. As the gelatin hardening agent for each layer, /-oxy-J,j-dichloroQ-s-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer so, e SO3H-N(C2H5)3 (halogenation @ per mole, f for large size emulsion
-14t, 0X10 moles, for small size emulsions! , tX10' moles) and (co, 0X10"-' moles each for large size emulsions and x, zxio moles each for small size emulsions) (per mole of silver halide*) hit, ff7.0x10 for large size emulsion
molar, also for small size emulsions /, 0X70-5
moles) (per mole of silver halide, 100 moles for large size emulsions, 1/, 1 for small size emulsions)
For the X10 morph red-sensitive emulsion layer, λ, t×io moles of the following compound were added per mole of halogenated bales.

added.

The following dyes were added to the emulsion layer to prevent irradiation.

And also for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer: /-(j-methylureidophenyl)-! - Each mercaptotetrazole is halogenated*1 per mole
．． lX10 mole, 7゜7X10 mole, co,
jX10 moles were added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, ≠-hydroquine-4-methyl-/, J, Ja, 7-titrazaindene was added per mole of halogenated chain, respectively, 1X10-'
Mol and CoX/117'Molar addition (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (N/m2). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti02) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion 0. JO gelatin
i, rt yellow coupler (
ExY) 0.12 color image stabilizer (Cpd-/)
0. / Solvent (Solv-/)
0.31 Color image stabilizer (Cpd-73o, o≦ 2nd layer (color mixing prevention layer) Gelatin Q, も? Color mixing prevention agent (Cpd-t) 0.Or solvent (Sol
v-/) 0. /4 solvent +8o1v-4A
) 0.01 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.j!μmL
% and 0. A l:3 mixture (Ag
molar ratio) 1 The coefficient of variation of the particle size distribution is a, 10 and o,
gelatin magenta coupler (EXMI color image stabilizer (cpd-1) color image stabilizer (cpd-j) color image stabilizer Agent (Cpd-≠1 Color image stabilizer (Cpd-ta) T?!a (S o l v-2) Solvent (Solv-74 Fourth layer (ultraviolet edge absorption layer) Gelatin Ultraviolet absorber (UV-71 Color mixture prevention'jill (Cpd-resolvent (8o1v-j) Fifth M (red-sensitive layer) Silver chlorobromide emulsion (cubic, mixture of one with an average grain size of 00j1 μm and one with an average grain size of 0.41!μm) (Ag molar ratio).The coefficient of variation of particle size distribution is o, oy and 0./
/, each emulsion contains 0.4 mol 96 of AgBr on the grain surface.
Station O, l +2 /, 2 reference 0.2- 〇, 0J O-/j O, Q λ 0, θ λ O, l reference 0.30 /, ! 0.23 gelatin
1. J≠Cyan coupler (Ex
ClO,J color image stabilizer tcpct-a)
0. /7 color fade stabilizer (Cpd-7)
0-30 Color image stabilizer (Cpd-r) o
, o4c solvent (Solv-4) 0. /j
6th layer (ultraviolet absorption layer) Gelatin 0°j3 ultraviolet edge absorption 11fll (UV-/) 0. / as a color mixing inhibitor (Cpd-j) 0,02+! ! ! Medium (S
olv-rn o, or 7th layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (IElf 77%)
o,ty liquid paraffin
0.03 (ExY) l:l mixture (molar ratio) with yellow coupler H3 Cz) (s (Ex M ) magenta coupler (ExC) cyan coupler C5I-1x (t) H3 C4H9 (c) General=C2H5 4H9 Coni 4c:Hiro mixture (Cpd-/) Coni:l mixture of color image stabilizer (molar ratio) (cpa-co) color image stabilizer<Cpd-J) color image stabilizer (Cpd-) Color image stabilizer (cpd-7) Color image stabilizer + CH2-CH- + a CONHC4Hs (t) Average molecular weight to, o C0 (Cpd-1) Color image stabilizer l l Mixture (Cpd-22 Color image stabilizer (Cpd-color mixture inhibitor (cpcl-+) Color image stabilizer C4Hs (t) C4H9 (t) +2 = Dust mixture (weight ratio) (UV-/) Ultraviolet absorber C5H41 (t > C4H9 ( t) C4H9(t) ginseng mixture (weight ratio) (S.

lmer l) molten Medium (Solv-Co) Solvent (Solv-4) Solvent Coni/Mixture (volume ratio) (Solv-Hiroshi) Solvent (Solv-7) Solvent C) 13 (8o1v-j) Solvent C00CsHt7 (CHHz)s (OOC6H17 H3 The sample prepared as described above (referred to as rot).

Subsequently, as shown in Table 5, a compound represented by the general formula (1) of the present invention was added to the third layer (green-sensitive layer) and its adjacent layer to prepare a sample.

After these samples were continuously treated with sample zoi according to Example 1, the performance of each sample was evaluated. evaluated. However, this treatment was carried out using the treatment steps and treatment liquid composition shown below.

Treatment process Temperature Time Replenishment amount 0 T/R capacity color damage 32°C! seconds yoMl ioi bleach-fix JZ'C reference j seconds /rOal II rinse 130°C 20 seconds rinse 2 1ouc --- rinse 3 30
'C2JOwl Drying rOoC for 0 seconds The amount of water per 1 m2 of photosensitive material Rinse: 3-tank countercurrent method from 3 to 1 The composition of each processing solution is as follows.

Color developer tank liquid m water
roost room
Polymers of the present invention o, zg o, tg (
Refer to Table J] Ethylenediamineteta, ug P, μg
Diethylenetriamine laphosphonate 1. Kog i-xg
Pentaacetic acid 1, Kodihydroquine O5≦go,≦yBenzene-2.6 Monodisulfonic acid Triethanolamine Sodium chloride Potassium bromide Potassium carbonate N-Ethyl-(β-methanesulfonamidoethyl)-3-Methyl-3 -Aminoaniline sulfate organic preservative (A-7) Sodium sulfite fluorescent brightener (Sumitomo Chemical WWHITEX-4) Add water to 1000 m 100 O Coj'
() 10-00 bleach-fix solution (common to tank solution and replenisher solution) Water 00w
Ammonium 1thiosulfateill (70o1/l)0
001d / / , jO 1j, 01i g lλ, Og 0, Ojmol 0. □rmol o, ig o, 2g i, og o, cog iz, og 1.0fi Q, OJ! 9 Discussion g z,og Ammonium sulfite l Ethyrefediaminetetraacetic acid iron (DI) Ammonium zzg Ethylene difudinetetraacetic acid ill Water'lk addition
iooomph (ko! 0C)
4.0 Rinse solution (common for tank solution and replenishment solution) Ion exchange water (calcium, magnesium jpE) m or less J See the results! Shown in the table.

Next, in the process, after the color development process, the bleach-fixing process, which is immediately followed by the desilvering process, was carried out using the method shown below, and the performance was evaluated in the same manner as before. I did it.

At this time, the color developer and rinse solution used previously were used as they were.

Recycling treatment process Temperature Time Replenishment amount 1 Tank capacity Color present time 3ri'C4Lj seconds 70d 10/Bleach-fix JroC+1 second CocoOal tr/su7s1 30oC20 seconds rinse 2 70℃ -m- Rinse 3 300C23 (Nd dry t o 'c Refill amount per second θ second cloudy photosensitive material/m Add 3 tanks of countercurrent photosensitive material from 3 to 1 for rinsing (
7m Add the following regenerant per over 70-liter liter of bleach-fix solution per process and adjust the pH with acetic acid! , 7 and used as a replenisher for the bleach-fix solution.

Tank liquid water 4AOO
Ammonium thiosulfate solution g (7oo9/l) / 0
014 Ni([2Ammonium lHiroI ethyrefdiaminetetraacetic acid iron(III) Ammonium zg Water 1-Additional 1ooovtpH(
λj'c) 4.7 Regenerant (per liter of tank liquid) Ammonium thiosulfate (70 t) Hiroshi/ , , <I
I/Ammonium sulfite! 39 Ethylenediami/Iron (In) Tetraacetate Ammonium 1411 The results obtained as above are also summarized in Table 5.

Table 1 shows that when a color photosensitive material containing a compound represented by the general formula (1) of the present invention is treated with a coloring liquid containing a water-soluble monomer, yellowish/magenta color images are produced. Significant improvements in fastness and photographic performance fluctuations during continuous processing are evident.

In addition, in a process in which a desilvering process is performed immediately after color development processing, and in a process in which all of the bleach-fixing processing solution in the desilvering process is recycled, the light fastness of yellow stain and magenta color images in comparison samples was particularly high. In contrast, there was no change in yellow stain, light fastness of magenta color images, or fluctuation in photographic performance during continuous processing in the samples that met the constituent requirements of the present invention, and a good improvement effect was observed. It is also clear that

(Effects of the Invention) A halogenated color photographic light-sensitive material containing a compound represented by the general formula CI) is processed with a color developer containing gold, an anionic group-containing water-soluble polymer, yellow stain/and color. It is possible to maintain improved light fastness of the image and to reduce fluctuations in photographic performance during continuous processing. In addition, even if a processing method in which a desilvering process is performed immediately after color development processing is implemented, the above-mentioned effect is produced, and even if rapid processing is performed, the same effect is obtained. Excellent nine effect gold shows.

Therefore, it is possible to provide a method for processing a color photographic material with improved staining after processing, light fastness of color images, and fluctuations in photographic performance during continuous processing.

Claims (1)

[Scope of Claims] 1. A method of processing a silver halide color photographic light-sensitive material after exposure with a color developing solution containing an aromatic primary amine color developer, wherein at least one of the silver halide color photographic light-sensitive materials is treated with a color developing solution containing an aromatic primary amine color developer. A silver halide color photographic light-sensitive material containing at least one compound represented by the following general formula (I) in a layer, and a water-soluble polymer containing a repeating unit having at least one anionic group in the color developer. 1. A method for processing a silver halide color photographic material, comprising processing with a color developing solution containing at least one of the following. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 may be the same or different and each represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, and R_3 and R_4 may be the same or different. each represents an alkyl group having 1 to 18 carbon atoms. 2. A silver halide color photographic photosensitive material according to claim 1, characterized in that in a processing method in which a desilvering step is carried out immediately after color development processing, an overflow solution of the desilvering step solution is reused. How materials are processed.