JPH0470653A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease staining by processing by processing the photosensitive material for which specific high boiling org. solvents are used with a color developer which has a specific water-soluble polymer, does not substantially contain benzyl alcohol and has a low concn. of sulfurous acid ion. CONSTITUTION:The silver halide color photographic sensitive material contains the dispersion of lipophilic coupler articles consisting of at least one kind of the high boiling org. solvents which are expressed by formulas I to III and do not substantially mix with water. The color developer contains at least one kind of the water-soluble polymers contg. repeating units having amide bonds. The sulfurous acid ions have <=8 X 10<-3> mol concn. per 1 liter color developer and do not substantially contain the benzyl alcohol. In the formulas I to III, W1 to W3 may be the same or different and respectively denote an alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group. The staining by processing is lessened in this way.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, the present invention relates to a method for processing silver halide color photographic materials. This invention relates to a method for processing photographic light-sensitive materials (hereinafter referred to as "photosensitive materials") that causes less staining after processing.

[Prior art]

From the point of view of environmental conservation, reducing the amount of photo processing waste is an important issue. In recent years, it has become possible to considerably reduce the load of photographic processing waste liquid in color developing solutions by carrying out low replenishment processing. However, by performing the above-mentioned low complementation treatment, the accumulation of oxidative decomposition products of the color developer composition,
Color developing solutions have become fatigued due to evaporation and concentration, which has caused many problems. For example, tar generated by oxidative decomposition products of the developing agent in the color developer can contaminate photographic processing machines, or it can adhere to the rollers used to transport photosensitive materials in the processing machine and transfer to the photosensitive materials, reducing the quality of the finished product. . Furthermore, finer colored components of the color developer generated over time penetrate into the photosensitive material, resulting in stains after processing.

A preservative has been proposed from the viewpoint of improving the preservative performance of color developers and preventing the generation of tar and staining of photosensitive materials. For example, US patent J/y/! Hydroquine carbonyl compounds described in No. 303 and British Patent No. 30A/7, JP-A No. 13020 and No. 1 Tsukasa!
3-α-aminocarbonyl compound described in Tori Hirokoyo issue,
Hydroxamic acids described in JP-A No. 52271.31 and hydrazines described in European Patent No. 02-21rOA2 are mentioned. Although some of these prevent the deterioration of the color developer to some extent, they are not very effective in preventing the generation of tar mentioned above.

It has been known for a long time that sulfite ions are effective in preventing tar in color developers and in preventing liquid coloring. However, when sulfite ions are used to process light-sensitive materials using high silver chloride for rapid processing in recent years, they cause significant inhibition of color development.

Therefore, conventional techniques cannot be said to be sufficient in improving the storage performance of color developing solutions and reducing contamination of photosensitive materials due to generation of tar and coloring of the solutions.

On the other hand, it is known that the water-soluble polymer containing a repeating unit having an amide bond according to the present invention is added to a color developer from the viewpoint of preventing crystal precipitation of a developing agent of the color developer. For example, special public show≠7-207g3, samej♂
-/l/7. However, these are used in systems containing sulfite ions, and there is no mention of contamination of photosensitive materials due to generation of tar or coloring of the liquid. It has also been found that these compounds alone do not solve the above problems at all.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to reduce the amount of sulfite ions.
Another object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which even if a color developer is not present, the light-sensitive material is less contaminated or "processing stain" due to generation of tar or coloring of the solution.

(Means for solving problems) The above objective was achieved by the following method.

That is, in a processing method for color developing a silver halide color photographic light-sensitive material, the silver halide color photographic light-sensitive material has the following - sterilization CA), CB) or [C]
The color developer contains a dispersion of lipophilic coupler particles consisting of at least one high-boiling organic solvent that is substantially immiscible with water represented by Contains at least / sulfite and has a sulfite ion concentration of ♂ per liter of the above color developer
This was achieved by a method for processing a silver halide color photographic light-sensitive material, which is characterized in that the amount of X10 is 3 mol or less and that it does not substantially contain benzyl alcohol.

General formula (A) General formula (B) W , represents a heterocyclic group.

Note that these groups include not only unsubstituted groups but also those substituted with other substituents.

Contamination of the photosensitive material due to the generation of tar and coloring of the color developer over time, especially "processing stains" caused by coloring components that penetrate the photosensitive material, must be distinguished from stains caused by color development in unexposed areas. That is, the former contamination is so-called "dirt" and can be removed, for example, by washing with acid. However, the latter stain is a color developed in the photosensitive material as a pigment and cannot be removed even by washing.

The present invention uses a color developer which contains a specific water-soluble polymer, substantially does not contain indyl alcohol, and has a low degree of sulfite ion IIk, and a photosensitive material using a specific high-boiling organic solvent. It is said that the above-mentioned "stain" can be significantly reduced by processing with. Considering the structure of the invention, it is thought that this "stain" interacts with the high boiling point organic solvent in the photosensitive material, and the effect of the above combination is interesting and noteworthy.

Here, the fact that the high boiling point organic solvent of the present invention is substantially immiscible with water means that its solubility in water is less than 5% by weight at 2!0C. Preferably it is 3% by weight or less.

In the present invention, the amount of high boiling point organic solvent used can be any amount depending on the type of coupler and the amount used.
Preferably, the weight ratio of the high boiling point organic solvent to the coupler is O,OS-coO.

Although it is sufficient that the color light-sensitive material has at least one emulsion layer containing the above-mentioned high boiling point organic solvent, it is preferable to have all the emulsion layers. More preferably, it is also used as a dispersion solvent for layers containing lipophilic substances other than emulsion layers.

Further, the high boiling point organic solvent of the present invention can be used alone or in combination of a plurality of compounds.

Further, compounds other than those specified in the present invention may be mixed and used as a high-boiling organic solvent within a range that does not impair the effects of the present invention.

Further, the dielectric constant of the high boiling point organic solvent is preferably 1.
A range of 7 to t, o is good.

Hereinafter, the compounds represented by general formulas (A) to (C) of the present invention will be explained in detail.

- In killing (A), (B), or (C), Wl,
When W2 and W3 further have a substituent, this substituent is 7
or two or more 100-1-CON, , -RN, (R represents a λ~V-valent group obtained by removing a hydrogen atom from a phenyl group) and -
It may be a group containing a linking group selected from 〇-.

In general formulas (A), (B), and #-1: (C),
The alkyl group represented by Wl, W2, or W3 may be linear or branched. For example, methyl group, ethyl group, propyl group, butyl group, bethyl group, hexyl group,
heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodel/l group, tridecyl group, tetradecyl group,
These include a pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eikonyl group.

The substituents that can be attached to these alkyl groups are
A] is an example of a halogen atom, a cycloalkyl group, an aryl group, or an ester group. Examples of such substituted alkyl groups include halogen (
F, Cl, Br) substituted products (-C2HF4, -C5H3
F8, -C2H3F10, -C2H4cml, -C3H
5Cg, -C3H502゜CaHs (JBr, -C3H
5B r 2, etc.), cycloalkyl C2H9 -CH2O (2α sword Cl2H25 Steh $ f given El place % (-()12 CH(
OH)-COOC6HI3 (CH=2-C00CH2(CF2CF2)2H1, etc.), tartaric acid ester, etc. Gold-giving groups -(CH2)7αC4H9 -(CH2)8C(-X)C4H9, etc.), Milk general formula CB ), also in [C], the same substituent in the alkyl group of the above-mentioned -killing CA) may be substituted with a substituent kyl group that provides an alkitic acid ester or the like.

Wl, W2, or Shifuroa represented by W3 Li, Substituted cyclohexynyl groups are e.g. CH3 These are the basics.

W 1, W 2, or the aryl represented by W3 Ali The group is for example etc.

The alkenyl group is -C4H7 C3H9 6H1) C7H13 C3H15 10H19 -C12H23 18H35 etc., Substituted alkenyl groups are e.g. (P-3 0==P(OC6H13n)3 P-G 2H5 (P-J-) replaced group, -CH=sign -COO-CH2CHC4H9(P Otsu ():P(OC8H17-n)3 As these high boiling point organic solvents are uninvented, The range of dielectric constant is More preferably 3 It's over 10.

0=P(OCH2CHC4Hg-n) J′O or less.

2H5 less than, General formula (A), (B) or (C) A specific example of a high boiling point organic solvent represented by The invention is not limited to these.

(P−/) 0=P (OC4Hg −n )3 (P 0==P(OCgHlg −n )3 (:P−/1) (P−7 o=p(ocn(a−i2)6O(3 )3C)(3 (P-/j) (P-/ (P-/3 H3 (P-/I) (P-/ri(P-/z) (P-λO) 2H5 P-27 (P λ3) (P-2≠) (P-λyo) (P-3 (P-32 (P-33) (P 31Lt) (P 3ri2H5 (P Koro) (P-2g) (P-27) (P -30 (P-3♂ (P≠O) H3 H3 (P-≠7) (P-≠2) COQC8H,7 (O42)8 COOC8H17 Contains a repeating unit having an amide bond of the present invention The water-soluble polymer will be explained in detail below.

The water-soluble polymer containing a repeating unit having an amide bond used in the present invention is as follows: (I), ([) or H (I
Those represented by II) are preferred.

-Satsu (1) In the formula, R1 represents a hydrogen atom or a lower alkyl group having a carbon number of /~≠, and R and R each represent a hydrogen atom or a carbon number/~g alkyl group (including substituted alkyl groups). , represents an aryl group (including a substituted aryl group) having 2 to 7≠ carbon atoms, and may be bonded to each other to form a ring structure.

To explain in more detail, R1 is a hydrogen atom, carbon number/~
≠ lower alkyl group (e.g., methyl group, ethyl group,
butyl group), and among these, a hydrogen atom and a methyl group are particularly preferred.

R2 and R may be different or the same, and each represents a hydrogen atom, an alkyl group having 7 or more carbon atoms (e.g., methyl group, ethyl group, hydroquinethyl group, butyl group, n-hexynyl group), carbon :56~/Hiro aryl group (for example,
phenyl group, methoxyphenyl group, chlorophenyl group)
Of these, a hydrogen atom, an alkyl group having a carbon number of ≠≠, and an aryl group having a carbon number of t to 10 are preferred, and a hydrogen atom, a methyl group, an ethyl group, and a hydroxyethyl group are particularly preferred. Furthermore, it is most preferable that at least one of R2 and R3 is a hydrogen atom.

Also, when R2 and R3 are combined with each other to form a ring structure, the ring formed is! Preferably, the ring has a ring structure of 4 to 7 degrees, and examples of particularly preferable ring structures include a pyrrolidine ring, a piperidine ring, a morpholine ring, and a piperazine ring. These ring structures formed may have a substituent.

General Formula (If) In the formula, R1 is the same as shown in the above-mentioned (1). R
4, R5 each represents a hydrogen atom, an alkyl group (including substituted alkyl groups) having carbon number/~r, or a group that combines with each other to form a lactam ring, oxazolidone ring, or pyridone ring (these ring structures are may have a substituent).

To explain in more detail, R4 and R5 may be different or the same, and include a hydrogen atom, an alkyl group having carbon number/~g (e.g., methyl group, ethyl group, hydroquinethyl group, butyl group, hekylene group). Group ), or bonded to each other ring @ number! ~7 lactam rings (γ-lactam, δ-lactam, ε-lactam), number of ring members! A group forming a total of 7 to 7 oxazolidone rings or a pyridone ring having j to 7 ring members is preferable. Among these, '#' is preferably a hydrogen atom, a methyl group, an ethyl group, or a case where the ring structure formed forms a pyrrolidone ring or an oxazolidone ring.

General formula (III) +CH2C+ In the formula, R is the same as shown in the above-mentioned (I).

Z represents an atomic group necessary to form a j to 7-membered ring structure. These ring structures may have substituents.

To explain in more detail, Z is preferably! Member ring or A
Represents atoms # required to form a ring structure of a membered ring (for example, a succinimide ring, a maconimide ring, a phthalimide ring, etc. as a ring structure to be formed), particularly preferably a ring structure to be formed. is the case of the scunnimide ring.

Preferred specific examples of the repeating unit having an amide bond used in the present invention are shown below, but the present invention is not limited to these examples.

moCH2CH+ moCH2CH-)-H20(++a-i2CH-)-CONHcH3C0NHC2H5 The water-soluble polymer containing a repeating unit having an amide bond of the present invention may be a homopolymer, and may have any λ It may also be a copolymer containing repeating units having three or more amide bonds.

Furthermore, copolymers with other ethylenically unsaturated monomers may be used as long as the solubility of the polymer in water or aqueous alkaline solutions is not impaired.

Examples of such copolymerizable ethylenically unsaturated monomers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid (such as methacrylic acid), and esters derived from these acrylic acids. (For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, λ-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, co-hydroxyethyl memethacrylate, β-alkoxyethyl (meth)acrylate (for example, co-methoxyethyl acrylate, λ-methoxyethyl methacrylate, λ-methoxyethyl acrylate, coethoxyethyl acrylate, coethoxyethyl methacrylate, cobutoxyethyl acrylate, 2-n-propyloxyethyl methacrylate, 2-(comethoxy)ethoxyethyl acrylate, etc.), β-sulfonamidoethyl (meth)acrylate, β-cal vinyl esters (e.g. vinyl acetate, vinyl laurate), acrylonitrile, methacrylate, dienes (e.g. butadiene, isoprene), aromatic vinyl compounds (e.g. evastyrene, divinylbenzene and its derivatives, e.g. vinyl toluene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (flJt
maleic anhydride, maleic ester, N-vinylpyridine, and co- and ≠-
Examples include vinylpyridine, ethylene, fluoropyrene, /--7tene, isobutyne, and the like.

Among these monomers, those whose homopolymers are soluble in water or aqueous alkaline solutions are preferred, and ethylenically unsaturated monomers having an anionic dissociative group are particularly preferred.

Examples of anionic dissociative groups include -COOH group, -803H
group, -8O2H group, -〇P(-OH)2 group (or its monoalkyl ester group), -0803H group, and the like. These anionic groups can be used in their respective salts, such as alkali metal salts (eg Na.

K salt), ammonium salt (for example, salt with ammonia, methylamine, dimethylamine, etc.).

An example of such an ethylenically unsaturated monomer having an anionic functional group is shown below in a non-dissociated form, but this is not intended to be limiting.

CH2=CH α) OCI(2CH20COCH2O(2COOH).

CH3 CH2=CH coo+button j coating C0OH.

a赳=CH C0NH(-CH2÷-COOH.

CH2=CH CH2-(:H CH3 C)f3 CH3CH2=C
00(2=C COOCH2CH20P-OH%C00CH2CH20
803HH The copolymerization ratio of the repeating unit having an amide bond of the present invention and the repeating unit derived from the monomer varies depending on the polarity, water solubility, etc. of the monomer component used, but in general, As a repeating unit having a bond, io to ioo mole, preferably 30 to ioo mole,
Particularly preferred is a range of jO to 100 mol.

The polymer or copolymer containing repeating units having an amide bond of the present invention can be synthesized using known methods such as solution polymerization, suspension polymerization, emulsion polymerization, precipitation polymerization, dispersion polymerization, and bulk polymerization. I can do it. For more information, see British Patent No. 1
Ko/103ri No., Tokuko Sho≠7-2ri No. 191, Tokuko Akihiro r-7jj No. 23, Douyu r-720λλ No., Tokuko Sho≠Turco//3≠ No., Tokuko Sho≠Turco/2043≠ No., British Patent No. 6/3 No. 5, U.S. Patent No. 3227672, No. 3 Lambda No. 3 O
't/7 issue, same 3λ otsukota/ri issue, same 32≠! No. 732, No. 2 Otsu rir'y'y, No. 323027! No., John C. Troboulos (John C, Petrop
``Official Digest J (Official Digest),
3 Described in Volume J, page 7/ri-73, 4 (/ri-ot/), "Synthetic Polymers" edited by Shunsuke Murahashi et al., volume 7, page 0 of Cog 4-2, volume 3, page /~iot, etc. This can be done by referring to the method. It goes without saying that the polymerization initiator, concentration, polymerization temperature, reaction time, etc. can be varied widely and easily depending on the purpose.

For example, polymerization is generally from 20 to /j00C.

Preferably, it is usually 0.06~ for the monomer to be polymerized at μo-12o'c! It is carried out using a radical polymerization initiator of a weight ratio. Examples of initiators include azobis compounds, peroxides, hydrochloride oxides, redox catalysts, etc., such as potassium persulfate, tert-butyl peroctoate, benzoyl peroxide, azobisisobutyronitrile, co-, 2'-azobiscyanokichi, etc. Grass acid, λ.

Examples include λ'-azobisu (2-amidinopropane hydrochloride).

When the polymer of the present invention is used as a copolymer containing a repeating unit having an amide bond, the copolymer may be a general random copolymer, a graft copolymer, or JP-A-Shojj-9-/17003
It may also be a block copolymer as described in JP-A No. 40-21) 0763.

The molecular weight of the polymer used in the present invention is usually about 20
00 or more. Preferably heθθO~2000000
A certain degree is used. However, these values are not critical to obtaining the effects of the present invention.

Specific examples of typical polymers used in the present invention are shown below, but the present invention is not limited to these specific examples.

0NH2 Example J Example 3 Gak + CI (20 (÷ C0NHCH20CH3 (-CH2CH÷ C0NHCH3 (-CH2CH÷ Example! Example C) (3 Example j Example ≦ Example 7 +CH2CH+ +CH2CH+ Example 10 Example // CH3 y:z=30:10 :60 (Molar ratio) (Molar ratio) (Molar ratio) Example/Example 15 Example/3 x:y:z=!0:10: HiroO (Mole ratio) x y Near j Koj (Mole ratio) Example /Ot a (3 examples/4t x:y:z=70:20:10 (molar ratio) x:y=rO: +20 (molar ratio) Contains a group primary amine color developing agent.

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

D-/N, N-diethyl-p-7 22renthia D-gu-J- D-♂ D-tamin 2-amino-! -diethylaminetoluene λ-aminoter(N-ethyl-N-laurylamino)toluender [N-ethyl-N-(β-hydroquinethyl)aminecyanilin comethyl-≠-[N-ethyl-N- hydroxyethyl)aminecyaniline≠-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl]-aniline N-(2-amino-!-diethylamino'phenylethyl)methanesulfonamide N,N -dimethyl-p-phenylenediamineμmamino-3-methyl-N-ethyl-N-methoxyethylaniline D-10≠-amine-3-methyl-N-ethyl-N-β
-ethoxyethylaniline D-// ≠-amino-3-methyl-N-ethyl N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, ≠-amino-3-methyl-h-ethyl N-[β-(methanesulfonamido)ethylcyaniline (Exemplary Compound D
-6) and λ-methyl-≠-[N-ethyl-N-(β
-Hydroxyethyl)aminecyaniline (Exemplary Compound D
-s).

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, p-)luenesulfonate, and the like. The amount of the aromatic-grade amine developing agent used is preferably in a concentration of about O1/g to about 20 g, more preferably about 0.1 g to about 0.1 g/jg/l of developer solution.

In the present invention, sulfite ion, which is conventionally known as a preservative for developing agents, is used in the color developer / L Yuutari J'X /
(It needs to be 7-3 moles or less.

More preferably, it is ≠×10 −3 mol or less. If the amount is more than n, the effect of the photographic performance will be poor, especially the degree of color development will be significantly reduced.Furthermore, if the amount is more than n, the effect of the present invention will not be fully manifested.

It has been found that when applying benzyl alcohol to color prints, tar buildup becomes noticeable over time, and even if the compound described in the present invention is used, it is not possible to prevent light-sensitive materials from staining. .

Therefore, instead of sulfite ion, it is preferable to use various organic preservatives to prevent oxidation of the developing agent. The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a light-sensitive material. In other words, they are organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same shall apply hereinafter), JP-A-4
Hydroxamic acids described in No. 3-143/31r, Otsu 3
-/l O≠/hydrazines and hydrazides listed in issue,
Phenols described in Otsu No. 3-μHiro Aj No. 7 and No. 63-5g≠≠3, α-hydroquine ketones and α-aminoguts described in No. A 3-u≠tSt, and 7. ;, It is preferable to add each of the saccharides described in No. 3-3, No. 2≠≠. In addition, when used in combination with the above compounds, % Kaisho 63
−≠23yo issue, ltsut3-+2<zxtg issue, same A3-
27Aa No. 7, 1.3-/IAI, O'AO No. 1, 1.3-/IAI, O'AO No. 1
．． No. 3-27141/, and A3-. 2! ;A! r≠
Monoamines described in No. 1.3-301 II
No. 6, No. 1.3-1lIAliO, No. 63-≠3/3
Diamino compounds described in No. 3, etc., polyamines described in No. t3-1ttss, A3-
1) - Polyamines described in No. utjj, t3-! 3!
;! ; Nitroxy radicals described in /, z3-≠3
7≠O, and alcohols described in A3-t3s Hiro issue, same 73-3tt! Oximes described in ≠ and 23
It is preferable to use the tertiary amines described in -λ3≠μ7.

The amount of the chemical compound added to the color developing solution is o, oo.
It is desirable to add it to a concentration of r mol/l-0,j mol/l, preferably 0.0j mol/l to 0.1 mol/l.

Particularly preferred is the addition of hydroxylamine derivatives and/or hydrazine derivatives.

Preferred hydroxylamine derivatives are those represented by the following formula (X/1).

General formula ('14) (In the formula, L represents a linear or branched optionally substituted alkylev group having 1 to 10 carbon atoms, and preferably has a carbon number of /~!.Specifically, methylene, ethylene Preferred examples include , trimethylene, and propylene. Examples of substituents include carboxy groups, sulfo groups, phosphono groups, phosphinic acid residues, hydroxy groups, and ammonio groups that may be substituted with alkyl. Preferred examples include a group, a postbox group, and a hydroxy group.A
is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amine group that may be substituted with alkyl (-), an ammonio group that may be substituted with alkyl, a carbamoyl group that may be substituted with alkyl, or a carbamoyl group that may be substituted with alkyl. Represents a good sulfamoyl group, carboxyne group, sulfo group,
Preferred examples include a hydroquine group, a phosphono group, and a carbamoyl group which may be substituted with alkyl. -L-A
Preferred examples include a carboxyethyl group, a carboxyethyl group, a carboxydipropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. A carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group can be mentioned as particularly preferred flu. R represents a hydrogen atom, a linear or branched optionally substituted alkyl group having up to 10 carbon atoms,
The number of carbon atoms/~j is preferred. Examples of substituents include carboxy groups, sulfo groups, phosphono groups, phosphinic acid residues, hydroxy groups, amine groups that may be substituted with alkyls, ammonio groups that may be substituted with alkyls, carbamoyl groups that may be substituted with alkyls, and alkyl groups. Represents an optionally substituted sulfamoyl group.

There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group,
A particularly preferred example is a phosphonoethyl group. L and R may be connected to form a ring. ) Next, specific compounds of the present invention will be described, but the compounds are not limited thereto.

(!3) (r4t) (j Rimata, as a hydrazine derivative, for example, European patent (E
The compounds described in PO22rlt, 210A2) are preferably used.

For the color developing solution that can be used without inventiveness, compounds shown in the following--Sterling IJ)) are more preferably used in order to improve the effects of the present invention.

-Satsuri CD) (In the formula, R1) is a hydroxyalkyl group with j-1 carbon atoms, R12 and R13 are each a hydrogen atom, an alkyl group with a carbon number of /~B, a hydroxyalkyl group with a carbon number of 2~B,
The Kandyl group, the id formula, and X' each represent a hydrogen atom, an alkyl group having 2 to 2 carbon atoms, or a hydroxyalkyl group having 2 to 2 carbon atoms. ) Preferred specific examples of the compound represented by -Killing CD) are as follows.

(D-/) Ethanolamine, (D,2) Jetanolamine, (D-,?) Triethanolamine, (D-μ)
Di-isopropanolamine, (D-t) λ-methylaminoethanol, (,D-4) u-ethylamineethanol, (D-7) u-dimethylaminoethanol, (D-,1') 2-) Ethylaminoethanol, (D-ta)/-diethylamine-2-propanol 3-diethylamino-/-propanol, 3-dimethylamino-/-propanol, isopropylamineethanol, 3-amino-/-propanol , co-amino-1-methyl-/, 3-propanediol, ethylenediaminetetraisopro-ξol, benzylethanolamine, co-amino-2-(hydroxymethyl)-/, J-prolcenediol, /,3-diaminopronominol, /, J-bis(2-hydroxyethylmethylamino)-proparal These compounds represented by the above-mentioned -killing [D] have the desired effect of the present invention per coloring solution/l (D-/ ,2
) (D-/j) (D-/Hiroshi) (D-/4) (D-/7) (D-tl) (D-/ri) (D-io) (D-//) (D- /l) It is preferably used in the range of 3g to 700g, and more preferably in the range of 4g-jOg.

The color developing solution according to the present invention has the following properties (E-1) and CE, since the effects of the present invention are better exhibited.
-II) is more preferably used.

General Section CE-I) R19, R20 and R21 each represent a hydrogen atom or an alkyl group having a number of carbon atoms of /~/r. However, R15
When represents -OH or a hydrogen atom, R14 is a halogen atom, a sulfonic acid group, an alkyl group having a carbon number of up to 7,
-0R18, -COOR19, -Sakatsu (E-1)) In the formula, R14, R15, R16 and R17 are each a hydrogen atom, a halogen atom, a sulfonic acid group, and a carbon atom number l
-7 alkyl groups, -oals, -COOR19, the alkyl groups represented by R14, R15, R16 and R17 include those with substituents, such as methyl group, ethyl group, 1so-propyl group, n-propyl group, Examples include t-butyl group, n-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, benzyl group, etc., and the alkyl group represented by R18, R19, R20 and R21 is as defined above, Further examples include octyl group.

Further, the phenyl group represented by R14, R15, R16 and R17 includes a phenyl group, a λ-hydroxyphenyl group,
Examples include ≠-aminophenyl group.

Typical specific examples of the chelating agent of the present invention are listed below, but the invention is not limited thereto.

(E-I-/) ≠-isopropyl/, cordihydroxyinzene (E-1-2) /, -dihydroxyinzene-3, yo-disulfonic acid (E-I-J) /, 2.3 -1-trihydroxybenzene-carboxylic acid (E-1-μ) /, λ, j -toIJ hydroxybenzene-j -carboxymethyl ester (E-1-3) /, λ, 3-trihydroxybenzene- yo-carboxy n-butyl ester (E-1-A) 1-1-butyl-/-2,3 trihydro-/be/
Zene (E-1-7) /, 2-dihydrox-7benzene-3. Hiroshi, 6-trisulfo/acid (E-II-/) 2.3-dihydroxynaphthalene-2-sulfonic acid (E-n-2) 2.3, r-trihydroxynaphthalene-2-sulfonic acid ■-3) co, 3-dihydroxynaphthalene-6-carboxylic acid (E-1)-μ) r, 3-dihydroxy-? -Isopropylnaphthalene (E-n-j) 1,3-dihydroxy-g-chlorona7-di(E)/-A-sulfonic acid Among the above compounds, compounds particularly preferably used in the present invention include /, λ- Dihydroxybenzene-3.
! -Disulfonic acid can also be used as an alkali metal salt such as sodium salt, potassium salt, etc. (Specific exemplary compound (E-■-2)).

In the present invention, the -killing CE-1) and CE-II
) is tmg~/per liter of color developing solution.
It can be used in the range of jg, preferably lmg
It is desirable to use the amount in the range of 10 g to 10 g, more preferably 26 mg to 7 g.

The color developer used in the present invention preferably has a pH of ~/2, more preferably ~//.

In addition, the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use a buffering agent for each food. Buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, 0
-Sodium hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate,! -sodium sulfo-hydroxybenzoate (!-sodium sulfosalicylate), potassium j-sulfo-λ hydroxybenzoate (j-potassium sulfosalicylate), and the like.

The amount of the buffer added to the color developer is 0.1 mol/1
or more, particularly o, imol/l, 0
, ! Particular preference is given to mol/l.

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

Specific examples are shown below, but the book is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediami/tetraacetic acid, triethylenetetraminehexaacetic acid,
Nitrilo = N, N, N-tris (methylenephosphonic acid)
, ethylenediami/-N, N, N', N
'-tetrakis(methylenephosphonic acid), i,3-diamino-2-pro, gnoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, /, cordiaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol Etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamineorthohydroxyphenylacetic acid, 2-phosphonobutane/2. ≠−
Tricarboxylic acid, /-hydroxyethylidene-/, /-
Diphosphonic acid, N, N'bis(2-hydroxybenzyl)ethylenediamine-N, N'-diacetic acid, catechol-3,≠, 2-trisulfonic acid, catechol-3,! −
Disulfonic acid! -Sulfosalicylic acid, goose sulfof
'J thylic acid.

These chelating agents are preferably ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, /, 3-diaminopro, o-nortetraacetic acid, ethylenediami/-N, N, N'
, N'-tetrakis (methylenephosphonic acid), and hydroxyethyliminodiacetic acid.

These chelating agents may be used in combination with 2 or more if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example /l
Hit 0. /g to about 10-g.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-14010 and No. 3
7-t9r7, 3l-71r21. No., μμ−/
No. 2310, Yoichita O/ri No. 2310, and U.S. Patent No. 3. ♂
/3. Thioether compounds represented by Ko≠No. 7, etc.
Tokukai Akira! λ-Hirori No. 222 and the same! 0-/! p-Finidine diamine compound represented by No. 31≠, JP-A-Sho! No. 0-73772z, Tokusho≠≠-3007≠,
Tokukai Shoj Otsu-/jlrl coro issue and jlrl j2-μ31λ
μ-class ammonium salts represented by No. 2, U.S. Pat. .

1), the p-amine phenols described in US Patent No. 2.
II';'4t, No. 903, 3. /2r, /II'λ
No. 4L, No. 230.7 FA, No. 3.2!3.

ri/ri issue, tvf Kimiaki≠/-7/≠37, US Patent No. U,! 12, j! No. 4, same j, jet, 924
No. and 3. j12. Amine-based compounds described in Ell, No. 37-itorr, ≠λkota 20/
No., U.S. Patent No. 3.7λI, 1) No. 3, Special Publication Sho≠/-/
/≠3/, same≠2-λ3♂Ir3 and U.S. Patent No. 3. ! 32. ! Polyalkylene oxide represented by No. 0/ etc., other/-phenyl-3-pyrazolidones,
hydrazines, mesoionic compounds, ionic compounds,
Imidazole, etc. can be added as necessary.

It is necessary that the color developer be substantially free of benzyl alcohol. "Substantially" means that the content is less than 0.0 ml per ip of color developer, and more preferably not at all. By substantially not containing it, fluctuations in photographic properties during continuous processing, particularly increases in staining, are small, and favorable results can be obtained.

Chlorine and bromide ions are necessary in color developers for purposes such as preventing capri. In the present invention, preferably the chlorine ion is /, O×10 −2 ~/, jf×
10 1 mol/l more preferably JrXlo-2~/X
Contains 10-1 mol/j. Chlorine ion # degree / , j
If it exceeds 10-1 mol/l, it has the disadvantage of delaying development.

In addition, staining cannot be prevented with λ, O x 10-2 mol/l, and furthermore, continuous fluctuations in photographic properties (especially minimum density) are difficult to achieve, which is the object of the present invention. This is not the book to achieve.

In the present invention, the color developer preferably contains bromine ions from 3.0×10 5 mol/l to 7.0×10 −3 mol/l. More preferably! , 0x10-5~!
×10−4 mol/l, more preferably /, 0×1
0-4 to ≠X/0-4 mol/l. Bromine ion a
When the degree is as high as /×10-3 mol/l, development is delayed, the maximum a degree and sensitivity are reduced, and J, θ×l0-5 mol/l
If it is less than 1, it is not possible to prevent staining, and furthermore, the photographic properties vary greatly due to continuous processing, and the object of the present invention cannot be achieved.

Here, chloride ions and bromine ions may be directly added to the developing solution, or may be eluted from the photosensitive material during in-situ processing.

When added directly to a color developer, chloride ion supplying substances include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride.
Among them, preferred are sodium chloride and potassium chloride.

Further, the optical brightener may be supplied in the form of a counter salt of the optical brightener added to the developer. As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide,
Examples include thallium bromide, of which potassium bromide and sodium bromide are preferred.

When eluting from the photosensitive material in the present state, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

In the present invention, in addition to chlorine ions and bromide ions, any antifoggant can be added as necessary. As antifoggants, Vi, alkali metal halides such as potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6
- Nitrobenzimidazole, j-nitroinindazole,! -Methylbenzotriazole,! -nitropenzotriazole, j-chloro-benzotriazole 2-
Typical examples include nitrogen-containing heterocyclic compounds such as +77'' lylubenzimidazole, -thiazolylmethyl-inzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains an optical brightener. As a fluorescent whitening agent, ≠, 4L'
-Diamino-J, 2'-disulfosterone type compounds are preferred. The amount added is O~10g/1) Preferably o,
/-jg/l.

Furthermore, various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer of the present invention is 10 seconds to /0 seconds,
Preferably, the effect of the present invention is significant in 20 seconds to 60 seconds. Also, the processing temperature is 33~Hiro! The effect of the present invention is particularly remarkable at 0C1, preferably from 3t to 0'C.

The replenishment amount of the color developer during continuous processing is λ0-2 0rrJ per m2 of light-sensitive material, preferably 0rrJ. ~/AOml
However, a volume of 30 ml to 10 ml is particularly preferable since the effects of the present invention can be effectively exhibited.

Aperture ratio (air contact area (cm2) of the color developer of the present invention
)/liquid volume (Cm3)) is preferably 0 to 0.7 cmt. Practically 0.00/~0 in continuous processing
．． The range is preferably 0.0,002 to 0.03 cm, and more preferably 0.002 to 0.03 cm.

It is generally known that when hydroxylamine is used as a preservative, decomposition occurs due to heat or trace metals even if the aperture ratio of the color developer is reduced. However, when the compound represented by the general formula (■) or the compound represented by the general formula (D) or (blind) according to the present invention is used in a color developer, the decomposition of these compounds is extremely small, and the color It is sufficiently practical even when the developer is stored for a long period of time or used as a replenisher for a long period of time. Therefore, in the case of such long-term use, the smaller the aperture ratio is, the more preferable it is, and the most preferable range is 0 to 0.002 an-.

In the present invention, desilvering treatment is performed after color development.

The desilvering step generally consists of a bleaching step and a fixing step, but it is particularly preferable that they are carried out simultaneously.

The bleach or bleach-fix solutions used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (eg, ammonium iodide).

If necessary, one or more inorganic substances having pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Acids, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely sodium thiosulfate,
Periosulfates such as ammonium thiosulfate; Thiocyanates such as sodium thiocyanate and ammonium thiocyanate; Water-soluble thioether compounds such as ethylene bisthioglycolic acid and 3,6-cythio-1,8-octanediol, and thioureas. These silver halide solubilizers can be used alone or in combination of two or more. It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, preference is given to using thiosulfates, especially ammonium thiosulfates. The amount of fixing agent per 1) is preferably 0.3 to 2 moles, more preferably 0.5 to 1. It is in the range of 0 mol.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 8 are preferred, and 4 to 7 are particularly preferred. p
If H is lower than this, the desilvering property will be improved, but the deterioration of the solution and the leucoization of the cyan dye will be promoted. On the other hand, if the pH is higher than this, desilvering is delayed and staining is likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) and other sulfite ion-releasing compounds. These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 2 to 0.50 mol/l, more preferably 0.04 to 0.40 mol/l. Particularly preferred is the addition of ammonium sulfite.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Sulfinic acids, carbonyl compounds, sulfinic acids, etc. may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

The bleach-fix solution of the present invention has a processing time of 10 seconds to 120 seconds, preferably 20 seconds to 60 seconds. Also, the replenishment amount is 30 mf to 250 m1 per liter of photosensitive material. Preferably 40m1-1
It is 50mf. Generally, an increase in staining and poor desilvering tend to occur as the replenishment amount is reduced, but according to the present invention, the replenishment amount of the bleach-fix solution can be reduced without causing such problems. be able to.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after fixing or desilvering treatment such as bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal on the Society on Motion.
Picture and Television Engineers (
Journal of the 5ociety of
, Motion Picture and Terevi
sion Engineers) Volume 64, p. 248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method of reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazoles, and chlorinated sodium isocyanurate described in JP-A No. 57-8542, and other benzotriazoles are also available. ”,
It is also possible to use the disinfectants described in the Sanitation Technique Complete Volume ``Sterilization of Microorganisms, Disinfection, and Anti-Mildew Techniques'' and the Japan Antibacterial and Antifungal Society's ``Encyclopedia of Antibacterial and Antifungal Agents.''

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9.
and preferably 5 to 8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 2 minutes at 15 to 45°C, preferably 25 to 45°C.
A range of 30 seconds to 1 minute and 30 seconds at 0°C is selected.

Even in such short-time water washing, according to the present invention, good photographic performance can be obtained without an increase in staining.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 58-1
No. 4834, No. 59-184343, No. 60-220
No. 345, No. 60-238832, No. 60-2397
All known methods described in No. 84, No. 60-239749, No. 61-4054, No. 61-1) 8749, etc. can be used. Especially 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-
A stabilizing bath containing 4-inchazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing process, a further stabilization process may be performed, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color solution until it exits the final bath (generally a water washing or stabilizing bath). The effects of the present invention can be significantly exhibited in a rapid treatment process in which the processing time is 30 seconds or less, preferably 3 minutes or less.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order. Furthermore, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the sensitizing 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 iodide chain content is 1 mole or less, preferably O12 mole or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same 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 layered 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 than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, mixed crystals are formed due to compositional differences, resulting in unclear boundaries. It is also possible to have continuous structural changes.

The light-sensitive material used in the present invention is a high-silver chloride emulsion containing 10 moles or more of silver chloride, and the silver chloride content of these high-silver chloride emulsions is preferably O mole or more, more preferably J mole or more. .

Such a high silver chloride emulsion preferably has a structure in which the localized silver bromide layer is provided 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 preferably has a silver bromide content of at least 10 moles, and more preferably exceeds 1.20 moles. And these localized layers are
It can be present inside the particle, at the edge, corner, or surface of the particle surface, but one preferred example is one in which evixaxial growth occurs at a part of the corner of the particle.

On the other hand, in order to suppress as much as possible the deterioration when the photosensitive 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 such cases, 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 0.1 μ to 2 μ.

The standard deviation of the particle size distribution divided by the average grain size) is preferably 20% or less, preferably 15% or less, so-called monodisperse emulsion. It is also preferable to use them by blending them in the same layer or to apply them in multiple layers.

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. In addition, it may be composed of a mixture of particles having various crystal forms. Among these, in the present invention, particles having the above-mentioned regular crystal form account for 50% or more, preferably 70% or more, and more preferably 90% or more. % 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 process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Ruthenium: Salts or complex salts of rhodium, palladium, osmium, iridium, platinum, etc. can be mentioned! In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is preferably from 101 to 10-t mol based on the silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral enhancement.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical exacerbation, see the lower right column on 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 sensitization is performed for the purpose of imparting spectral sensitization in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. It is preferable to add a spectral enhancing dye to an absorbing dye. Examples of the spectral enhancing dye used in this case include F. M. Har+mar) 1
eLerocyclic compounds-Cya
nine dies and related com
pounds (John Wiley & 5ons
(New York, London 3 Publishing, 1964
2013). Examples of specific compounds and spectral enhancement methods are described in the above-mentioned Japanese Patent Application Laid-Open No. 6
2-215272 specification, page 22, upper right column to 3rd page
The one described on page 8 is 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. Specific examples of these compounds can be found on page 39 of the specification of JP-A No. 62-215272. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface, or It may be any type of so-called internal latent image type emulsion in which latent images are mainly formed inside the grains.

When the present invention is applied to a color light-sensitive material, the color light-sensitive material includes a yellow coupler and a magenta coupler that form yellow, magenta, and cyan colors respectively by coupling with an oxidized product of an aromatic amine color developer. and cyan couplers are commonly used.

Cyan couplers, magenta couplers, and yellow couplers preferably used in the present invention are as follows: (C7-1), (C-■), CM-I), (M-II
) and (Y).

One-minute λ formula (C-■) H-catalytic formula <c, -n> General formula (Y) H Yt General formula (M-I) General formula (M-n) General formula (C,-1) and (C,-1)), R
,, R1 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R,, Rs and R6 represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R3 may represent a group of nonmetallic atoms that together with R8 form a nitrogen-containing 5- or 6-membered ring,
yl and Yz represent a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized developing agent; n represents 0 or 1;

Rs in the general formula (C, -n) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tart-butyl group, cyclohexyl group, cyclohexylmethyl group, Examples include phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by (C, -1) or (C, -II) are as follows.

Preferred 1) in general formula (Cy-I). is an aryl group or a heterocyclic group, including 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, a sulfonyl group, a sulfamide group, an oxycarbonyl group, and a cyano group. More preferably, it is an atomyl group substituted with a group.

- When IhaRz does not form a ring in Cy-1, R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R2 is preferably It is a hydrogen atom.

In the FQ formula (Cy I[), R is preferably a substituted, particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C, -n), preferably Rs has 2 carbon atoms.
It is a methyl group having a ~15 alkyl group and a substituted tA group having 1 or more carbon atoms, and the substituents include an arylthio group,
Arylthio group, acylamino group, aryloxy group,
Alkyloxy groups are preferred.

- In Cy-n, R1 is more preferably an alkyl group having 2 to L5 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

- Preferred R4 in saccharine (c, -n) is a hydrogen atom or a halogen atom, with chlorine atom and fluorine atom being particularly preferred.
Preferred Yl and Yt are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (M-I), R1 and R9 represent an aryl group, R represents a hydrogen atom, an aliphatic or aromatic group, and Y represents a hydrogen atom or a leaving group.

Aryl group (preferably phenyl group) of R1 and R9
The substituents allowed for substituent R1 are the same as the substituents allowed for substituent R1, and when there are two or more substituents, they may be the same or different e R1 is preferably a hydrogen atom, a It is an acyl group or a sulfonyl group of the class group, and particularly preferably a hydrogen atom.

Preferred Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in U.S. Pat.
Particularly preferred are sulfur atom dissociative types such as those described in No. 51,897 and International Publication No. WO88104795.

In the general formula (M-II), RIG represents a hydrogen atom or a disubstituted group; aYa represents a hydrogen atom or a leaving group; a halogen atom or an arylthio group is particularly preferred; Za;
Zb and Zc are methine, substituted methine 1, N- or -
It represents NH-, and 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, R1° or Y4, including when it is part of an aromatic ring!
In addition, when Za, zb or Zc is a substituted methine, the substituted methine may be used to form a multimer or more than a comer.

Among the pyrazoloazole couplers represented by the general formula (M-n), US Patent No. 1 is preferred in terms of low yellow sub-absorption of the coloring dye and light fastness.

The imidazo[/,s-,b]pyrazoles described in U.S. Pat. ≠0゜63≠
Pyrazolo (V, j-b) (/.

-9≠]triazole is particularly preferred.

In addition, a branched alkyl group as described in JP-A/-4r2IIj is directly connected to the 2.3 or 4-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A/-4j24tt. pyrazoloazole couplers containing a sulfonamide group in the molecule, such as those described in Japanese Patent Application Laid-Open No. ) No. 224. ! ≠
It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 1, No. 7rj.

- In sacrifice (Y), R1) represents...a rogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, and R12 represents a hydrogen atom,...a rogen atom or an alkoxy group. A is -NHCOR13, -NH8O2-R
13, -8o2NHR13, -C00R13, -802
Represents N-R13. However, R13 and R14 each represent an alkyl group, an aryl group, or an acyl group.

Y5 represents a leaving group. The substituents for R12, R13, and R14 are the same as the substituents allowed for R1, and the leaving group Y5 is preferably of the type that leaves with either an oxygen atom or a nitrogen button; Particularly preferred is the nitrogen atom detachment type.

The above-mentioned couplers represented by Cy-[) to (Y) are usually contained in the silver halide emulsion layer constituting the photosensitive layer in an amount of F)0. /~l.

It is contained in an amount of 0 mol, preferably o, i to O0j mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a polymer (eg, US Pat. No. 203.7/4) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Preferably, the homopolymers or copolymers described on pages 1 to 30 of International Publication WOr Jr. 10o7 Co. 3 are used, and acrylamide polymers are particularly preferred from the viewpoint of color stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminephenol derivative, a gallic acid derivative, an ascorbic acid derivative, or the like as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, t
-Hydroxychromans! -hydroxycoumarans,
Spirochromans, p-flufxiphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, amine phenols, hindered amines, and the phenolic hydroxyl groups of these compounds are silylated and alkyl Typical examples include ether or ester derivatives. Also, (bissalicylaldoximado) nickel complex and (bis-N,N-dialkyldithiocarbamide)
Metal complexes such as nickel complexes can also be used.

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

Hydroquinones are disclosed in US Pat. No. 1, 340. Jyo issue,
Same No. 2, 41/I, 413, Same No. 2, 7oo, Hiro! 3
No. 2,70/, /ri No. 7, No. 2.721, A
No. 41, No. J, No. 732,300, No. 2,733.
No. 76J, same No. 3. ri rλ, Tadahiro issue, same number ≠, ≠ 30
．． ll-21, British Patent No. 1.343, RI2/No.
U.S. Patent No. 1, 710.1rO1, U.S. Patent No. 2. tit
, No. 021, etc., t-hydroxychromans,! -Hydroxycoumarans and spirochromans are covered by U.S. Patent No. 3
゜4L32,300, same No. 3.67J, No. 030,
Same 3rd. j7≠, Bukoa issue, same No. J, tri l, Rioy issue, same No. J, 7G4L, No. 337, Tokukai Shoj Ko/! 2
2λj, etc., spiroindanes are disclosed in U.S. Patent No. 3,
p-alkoxyphenols are disclosed in U.S. Patent Nos. 1,73j and 7Aj, and British Patent No. 2. ott
,ri7! Issue, Tokukai Shojta IO! No. 32, Special Public Showa J7-
Hindered phenols are disclosed in U.S. Patent No. 3゜700, ≠Yo No. 5, and Japanese Patent Application Publication No. 76J.
No., U.S. Patent Office, λ1.23! No. Tokko Akira! 2-66
No. 23, etc., gallic acid derivatives, methylenedioxybenzenes, and amine phenols are disclosed in U.S. Pat.
No. 4Aj7,07, No. ≠, 33x, trt, Special Publication Showa Zt-xllata No. /3! No., Same No. ≠, Coro! ,
! British Patent No. 3, Jug, 1) No. 9, British Patent No. 1, Jilt, J/J, British Patent No. 1. ≠10,1r4
No. 6, Special Public Shoj/-/≠Ko No., Special Public Sho! ! −／／≠0
No. 36, same number! TarrJrttt No. J Turf 13
No. 1714, etc., single-metal complexes are disclosed in U.S. Patent No. ≠, 020.
No. 23r, No. μ, 2≠i, its, British Patent No. 2.
O Core, No. 731(A), etc., respectively. These compounds are usually for their corresponding color couplers! The purpose can be achieved by co-emulsifying with the coupler and adding it to the photosensitive layer in an amount of from 700% by weight. In order to prevent the cyan dye from deteriorating due to heat and especially light, it is 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. Patent No. 3, !33.7
2μ), ≠-thiazolidone compounds (e.g., US Pat. No. 3,3/A).

72j, 3!2.61J), benzophenone compounds (for example, those described in JP-A No. 6-27R),
4L), cinnamate ester compounds (for example, U.S. Patent No. J, 70!r, 10J, f, J,
707. Juri No. 5), butadiene compounds (
U.S. Pat.
．． ≠ No. 04,070, No. 777.47, 2 and No. 307, No. 04,070) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

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

It is also preferred to use, in particular, the following compounds in conjunction with the above-mentioned couplers. Particularly preferred is the combination with a pyrazoloazole coupler.

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 the occurrence of staining and other side effects due to the formation of colored pigments due to the reaction between the color-forming herbal drug or its oxidized product remaining in the film and the coupler.

A preferable compound (F) has a second-order reaction rate constant with p-aningine of 2 (in trioctyl phosphate at tOoC) of /, 01/mol-sec~/x
/0-51/mol-sec. In addition, the second-order reaction rate constant is JP-A-6J-/!
r! ≠! It can be measured by the method described in No.

When k2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent.

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

General formula (FI) Ri (A)nX General formula (Fn) R2-C=Y In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents/or 0. A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes the addition of an aromatic amine developing agent to the compound of general formula (FIG) represents a group that Here R1 and X.

Y and R2 or B may be bonded to each other to form a cyclic structure. Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (Fl) and (FII), see JP-A No. 63-1) No.
rsssr issue, European Patent Publication λrit3co/issue, 277
! Those described in the specifications such as No. r are preferable.

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. ).

General formula (GI) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. -Compound represented by riZ (G1)/riZ is Pearson's nucleophilic nCH3I
Value (R,G, Pearson, et al.

J, Am, Chem, Soc, ri0. J/Y(/ria
, r )) is preferably 5 or more, or a group derived therefrom.

For specific examples of compounds represented by the general formula (GI), please refer to the European Publication IP! Fken No. λj17λ, Tokukai Showtx-
ip, 1o4tt issue, JJ-12F/4'j issue, Tokugansho&j-/Jj7ko≠ issue, same 6ko 2/4t4r/ issue,
Preferably, those described in European Patent Publications Kota I'J Co/No. 7Sr and the like are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication Core No. 7jtr.

The photosensitive material produced using the present invention contains water-soluble dyes or dyes that become water-soluble through photographic processing as filter dyes in the hydrophilic colloid layer or for purposes such as preventing irradiation and halation. You may do so. Such dyes include oxonol dyes, 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 light-sensitive 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 method for producing gelatin are described in The Macromolecular Chemistry on Gelatin, written by Arthur Vuis (Academic Press, published in 2010).

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

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include 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. Examples include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with reflective layers or reflective materials, such as glass plates, polyesters such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate. There are films, polyamide films, polycarbonate films, polystyrene films, vinyl chloride resins, etc.

As other reflective supports, supports having a specular reflective or second type diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.05 in the visible wavelength range.
The above is preferable, and it is also preferable to roughen the metal surface or use metal powder to make it diffusely reflective. The metal may be aluminum, tin, silver, magnesium, or an alloy thereof, and the surface may be a surface of a metal plate, metal foil, or thin metal layer obtained by rolling, vapor deposition, plating, or the like.

Among these, it is best to obtain the metal by vapor depositing it on a book or other substrate. Preferably, a layer of water-resistant resin, particularly thermoplastic resin, is provided on the metal surface. It is preferable to provide an antistatic layer on the side of the support of the present invention opposite to the side having the metal surface. For details of such supports, see, for example,
3μ6 issue, t3-21st issue 7, same AJ-2412j/
No. 63-2≠KoJj, 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 a
It is preferable to use one treated with a ≠hydric alcohol.

Occupied area ratio of white pigment fine particles per defined unit area (C%) Fi, most typically the observed area is divided into adjacent unit areas of 6 μm x 4 μm and projected onto that unit area. Occupied area ratio (%) of fine particles (Ri)
It can be determined by measuring.

The coefficient of variation of the occupied area ratio (ch) is the average value of Ri - (R
) can be determined by the ratio s/R of the standard deviation of Ri to $. Number of target unit areas (n”) F
i4 or higher is preferred. Therefore, the coefficient of variation S/R can be determined by:

In the present invention, the coefficient of variation of the occupied area ratio (%) of pigment fine particles is O1/! Below and <1g knee 0. /2 or less is preferable. In the case of o, or or less, the dispersibility of the particles can be said to be "substantially uniform."

The present invention will be explained in detail in the following examples, but the present invention is not limited to the following embodiments.

During implementation: A multilayer color photographic paper having the layer structure shown below was prepared on a paper support which was double-sided laminated with polyethylene and whose surface was subjected to corona discharge treatment. The coating solution was prepared as follows.

! /Layer coating solution preparation: Yellow coupler (ExY) 0, Og and anti-fading agent (Cpd-/) Jr, 0g and ethyl acetate/! O
cc and solvent (Solv-j)/, Occ and solvent (Solv-a) J, Occ were added and dissolved, and this solution was added to a 10% gelatin aqueous solution containing radodecylbenzenesulfone pt o cc. rear,
Disperse with an ultrasonic homogenizer, and the resulting dispersion,
Silver chlorobromide emulsion containing the following blue-sensitive sensitizing dye (silver bromide 0
．． A first layer coating solution was prepared by mixing and dissolving 7molti)≠20g.

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, ti/!
-Bis(vinylsulfonyl)ethane was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer: Anhydro! , j’-jik o.

-J,J'-disulfoethylthiacyanine hydroxide green-sensitive emulsion layer; anthrotherethyl-! , j'-diphenyl-3.37-cisulfoethyloxacarpocyani/hydroxide red-sensitive emulsion layer: J,! '-diethyl methoxytheta, //-neopentyl thiadicyl cyanine iodide The following substances were also used as stabilizers for each emulsion layer.

The following dyes were used as anti-irradiation dyes.

[3-carboxy-5-hydroxy-gu (3-(3-
Carboxy! -oxo/-(λ,!-bisulfonatophenyl)-λ-pyrazoline-μm ylide/)-/-zorobenyl)-/-pyrazolyl] ?-dihydroxidita, 10dioxo-3,7-cissulfonatoanthracene-/,j-diyl)bis(aminomethanesulfonate)-tetrasodium salt [3-cyano-!-hydroxy-≠-(3-(3- Cyano-j-oxo-/-(gousulfonate phenyl)-
λ~pyrazolin-l-ylidene)-7-pentanyl)-
/-hyrazolyl]benzene≠-sulfonate-sodium salt (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2). The silver halide emulsion represents the coated amount in terms of silver.

-th layer (blue-sensitive layer) Gelatin / , J'g Silver chlorobromide emulsion mentioned above (0.7 mole of silver bromide) O1) g Yellow Turnip 7- (ExY) 0.6 g Antifading agent (cp
a-/) 0. /g color mixing inhibitor (Cpd-,
2) Solvent (Solv-J) Solvent (8o1v-4L) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-2) Solvent (Solv-/) Solvent (Solv-2) Third layer (green sensitive layer) ) Silver chlorobromide emulsion (silver bromide/, Tamorchi) 0.03g 0,rg O,0tg O,03g 0.0/jg 0.01)g 0,jg Magenta coupler (ExM) Anti-fading agent (Cpd- J) Anti-fading agent (cpct-μ) Solvent (Solv-/) Solvent (SOIV-2) Fourth layer (anti-color mixing layer) Gelatin anti-color mixing agent (cpct-μ) Ultraviolet absorber (UV-/) 0.3+2g 0.27 0, / 7 0.10 0, +2 0.03 / , 70 0.0tj 0, li! Ultraviolet absorber (UV-2) 0.23 solvent (
Solv-/) 0. Oj solvent (Sol
v-2) 0. or 5th layer (red-sensitive layer) Silver chlorobromide emulsion mentioned above (A g B r≠molecular, cubic, average grain size o, rμm) Gelatin cyan coupler (ExC-/Cyan coupler (ExC-2) Fading prevention Agent (Cpd-/) Solvent (Solv-/) Solvent (Solv-2) Color accelerator (Cpd-t) Sixth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-/) Ultraviolet absorber (UV-co ) Solvent (Solv-/) Solvent (Solv-2) 0.2 / /, IO ) O, Cot ) 0. /λ 0 , +20 o, it 0.0ri0 , / ! 0.70 0.2t O,07 θ, JO θ, O 7th layer (protective layer) Gelatin (ExY) Yellow coupler/ , O7 (ExC-/)-Cyan coupler α (ExC-2) Cyan coupler (ExM ) Magenta coupler (Cpd-/) antifade agent average molecular weight to, oo.

(Cpd-2) Color mixing prevention agent! -G-tert-octylhydroquinone (cp
a-J) Anti-fade agent 7.7'-dihydroxy-μ, Hiro, μ', ≠l-tetramethylco, λ'-spirochroman (Cpd-≠) Anti-fade agent N-(≠-dodecyloxyphenyl)-morpholine ( Cpd-j) Color development accelerator p-(p-) luenesulfonamito) phenyl-dodecane (Solv-/) Solvent See Table 1-7 (Solv-u) Solvent See Table 1-7 (8o1v-J) Solvent See Table 1-7 (8o1v-4C) Solvent See Table 1-7 (UV-t) Ultraviolet absorber Co(2-hydroxy-J, J-di-tert-amylphenyl)benzotriazole (UV-λ) Ultraviolet light Absorbent Co(J-hydroxy-J, j-tert-butylphenyl)benzotriazole The samples obtained in the above manner are summarized in Table 1-7.

! /-/table *Comparative compound Next, the following treatment solutions were prepared.

The prescription is as follows.

Water-soluble polymers with colored liquid-water amide bonds (see Table 7-2) Ben/zyl alcohol (see Table 1-2) Diethylene glycol (see Table 7-2) Diethylenetriaminepentaacetic acid N, N, N - Tetrakis (methylene phosphonic acid) 0.1g 0mJl 1) ml Og /-Hydroxyethylide/- /, /-diphosphonic acid triethanolamine Potassium chloride Potassium bromide Anryopotassium Fluorescent brightener (W ) (ITEX $B Sumitomo Chemical) Sodium sulfite N,N-diethylhydroxylamine N-ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-q-amino O, μg /+2.0g /, jg O, 0/g core, 0g/, Og 0.1g Hiroshi, Og pH (Corr'c) 10. or bleach-fix solution water 4oom
l ammonium thiosulfate (yoog/l) 100ml ammonium sulfite ethylenediaminetetraacetic acid iron (III) ammonium ethylenediaminetetraacetic acid ammonium bromide 410g jg 5g google Add water and ioomlpH (
Jj'C) (with acetic acid and aqueous ammonia)! , r Stabilizing solution (tank solution and refill solution are the same) Formalin (37%) Formalin-sulfite adduct -chloro-2-methyl-≠ 1 inch azoline-3-one 1-methyl-≠-isothiazoline-3-one Add water 0.1g 0.7g 0.02g 0.0/g 1000mlj pH (2j'c) ≠, 0
The color working solution obtained above was placed in a beaker to an aperture ratio of 0.
0/Cm-1 and aged for 10 days at 1 LtOOC. After aging, the color filter sample 10/
~iot was exposed through an optical wedge to 2 tocM, 8, and processed using the following processing steps.

The processing steps are as follows.

Processing process Temperature Time color present @Jj0C≠j seconds bleach fixing 3j0C≠! Stable for seconds ■ Stable for 3z0cO seconds ■ Stable for 3j'c2o seconds ■ Dry for 3!0020 seconds Minimum concentration (Dmi) of the processed sample obtained as above
n) was measured. As a further K filtration test, the color current liquid after aging is Toyo 1 grade! The colored matter on the paper and the state of the P solution were sensory evaluated.

(◎No tar material, 02 paper has a slight yellow to light brown color, ∆There is some blackish tar colored material, and there is liquid layer color, but it is transparent.X Liquid layer color is not very transparent. (or tar adheres to the top surface of the paper.) The results are shown in Table 1-2.

According to Table 1-2, the presence or absence of a water-soluble polymer having an amide bond slightly improves the D min and r excess test evaluations (A/-)A≠, &ko→bangj) Or (A
J→&6), if the high boiling point organic solvent or benzyl alcohol has a configuration other than the one according to the present invention, sufficient effects cannot be obtained. On the other hand, according to the configuration of the present invention, Dmin after processing
It can be seen that excellent performance can be obtained, with low tar resistance and a little staining caused by processing. (47,70~lt) (Example 2) Sample 10/ and ior prepared in Example 1 were treated in the same manner as in Example 7. However, the water-soluble polymer having an amide bond and sodium sulfite in the color developing solution were changed as shown in Table 2, and benzyl alcohol and diethylene glycol were not contained.

Dmin was measured in the same manner as in Example 7, and the maximum bulk density (Dmax) of yellow, magenta, and cyan was also measured. Display the results on a second screen.

As is clear from Table 2, in the absence of a water-soluble polymer having an amide bond, Dmaxi increases as sodium sulfite decreases, but Dmin significantly increases. (16/1)/7, /r) On the other hand, in the case of a water-soluble polymer having an amide bond, Dmax increases as sodium sulfite decreases, and Dmi
It can be seen that n does not increase and the film has good performance, that is, performance with less processing stains.

(21% λ, 3) Example 3 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.

Preparation of coating solution for the first layer Yellow coupler (ExY) /g, color image stabilizer (Cpd-/)≠,≠g and color image stabilizer (cpct-
7) Add 17.2 cc of ethyl acetate and solvent (S
olv-/)♂, 1g was added and dissolved, and this solution was heated at 10C.
It was emulsified and dispersed in an aqueous solution of tizelatin containing 4 sodium dodecylbenozene sulfonate IJ rcc/Ijcc. On the other hand, silver chlorobromide emulsion (cubic, average grain size o
, 3-near mixture of rr μm and 0.70 μm (silver molar ratio).

The variation coefficient of grain size distribution is 6 o, or and o, io, each emulsion contains 0.2 mol of silver bromide locally on the grain surface), and the following blue-sensitive sensitizing dyes are added to dog-sized emulsions per 1 mol of silver. For small-sized emulsions, λ and 0 x l0-4 moles were added, respectively, and for small emulsions, sulfur was increased and sulfur was added after adding λ and j x 10-4 moles, respectively. Mix and dissolve your own milk and this emulsion, ↓゛)
A first coating solution was prepared to have the composition shown below.

The coating solution for the second Nη· and other seventh layer phases was also prepared in the same manner as the first layer gold cloth solution. The gelatin hardening agent for each layer is /-
Oki 7-3. j-dichloro-5-triazi/sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Night-sensitive emulsion layer (per mole of silver halide, dog-sized emulsion (2.0 x 10-4 mol each for still small emulsions, !, j x 10-4 mol each) green-sensitive emulsion layer (per 7 moles of silver halide, 7.θ×/θ−5 moles for dog size emulsions and // for small size emulsions)
, 0x70-5 mole) red-sensitive emulsion layer (per mole of silver halide, ≠, 0x10-4 mole for dog size emulsions, j for small size emulsions, &
x 10-4 mol) and (per mol of silver halide, 0.1 x 10-4 mol for dog-sized emulsions, and / for small-sized emulsions)
, /x10-4 mol) For the red-sensitive emulsion layer, the following compound was added to 1 mol of silver halide or 2. t×10 −3 mol was added.

For the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, /-(j-methylureidophenyl)-j-mercaptotetrazole was added per mole of silver halide, respectively.
, r×10-5 mol, 7°7X/0-4 mol, 2. j
x10-4 mol was added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, thydroxy-6-methyl-/, 3.3a, and 7-tetrazaindene were added per mol of silver halide, i×1o-4 mol and jXlo-4, respectively. Mol added.

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

and (layer structure) The composition of each layer is shown below. The numbers are coating amount (g/m2)
represents. 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)] -th layer (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 gelatin / 1 O Yellow coupler (ExY) 0.12 color image stabilizer (Cpd-/
) 0. / Solvent (Solv-/)
0.3! Color f-image stabilizer (, cpa-7)
0. Ot; Second layer (color mixing prevention layer) Gelatin 0. Tata color mixing inhibitor (Cpd-r) o, or solvent (Solv)
-/) 0. /6 Solvent
0. Or third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, /:3 mixture (Ag molar ratio) of one with an average grain size of 0.55 μm and one with an average grain size of 0.32 μm. Coefficient of variation of grain size distribution is 01) 0 and 0.0
g, each emulsion had AgBr0. g-molti was locally contained on the particle surface. ) 0. /2 gelatin /, 2≠magenta coupler (ExM) 0.20 color image stabilizer (Cpd-
,2) 0.03 color image stabilizer (Cpd-3)
0, / Evening color image stabilizer (Cpd-4L)
o, or color image stabilizer (cpct-ta)
o, o cosolvent (Solv-, 2)
0. a0 Fourth layer (ultraviolet absorption layer) Gelatin /, Jr ultraviolet absorber (U~'-/) 0. ≠7 Color mixture prevention agent (cpa-t) 0. Or solvent (
Solv-j) 0. λμ fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, mixture of one with average grain size 0.3 gμm and one with O1≠jμm (Ag molar ratio). Coefficient of variation of grain size distribution are 0.09 and 0./
/, each emulsion has AgBr0. 23 Seratin / 34t cyan coupler (ExC) 0.3.2 Color image stabilizer (
Cpd-A) 0.17 color image stabilizer (Cpd
-7) 0. ≠θ color image stabilizer (cpa-♂)
o, ot, as solvent (SOIV-3)
0. /! Sixth layer (ultraviolet absorbing layer) Gelatin 0.33 ultraviolet absorber ([JV-/) Color mixing inhibitor (Cpd-j) Solvent (Solv-j) Seventh layer (protective layer) Gelatin Privinyl Alcohol (Modification degree/7 %) Liquid paraffin 7,33 acrylic modified copolymer O, 770,03 (ExY) Yellow coupler, / O, 0+2, O♂ (Ex~1) Magenta coupler /: /Mixture (molar ratio) /: /Mixture (molar ratio) (ExC) 2 by weight of each of Noah/Coupler a Mixture of Gugu (Cpd-/) Color image stabilizer (Cpd-j) Color mixing inhibitor (cpa) +2 of color image stabilizer : ≠ Hiro mixture (weight ratio) (cpct, 2) Color image stabilizer (cpa 3) Color image stabilizer (Cpd-≠) Color image stabilizer (Cpd-7) Color image stabilizer average molecular weight IO 1θOθ (Cpd -lr) mixture of color image stabilizer (Cpd-ta) color stabilizer (UV-/) mixture of ultraviolet absorber (weight ratio) Samples in which Solv was changed as follows: &ko0/~
KoO! It was created.

*The same comparative compounds a, b, and c used in Example-/ were used.

Next, the following treatment solutions were prepared.

Color developer tank liquid replenisher water
700ml 700ml) Water-soluble polymer of the present invention (see Table 3) 0.6g O, 3g diethylenetriaminepentaacetic acid O1≠g O, μgN, N,
N-tetrakis (methylenephosphonic acid) t, t, og ≠, Og/
, Kodihydroxybenzene≠.

6-Disulfonate sodium salt Triethanolamine Potassium chloride Potassium bromide Potassium carbonate Fluorescent brightener (WHITEX Part B Sumitomo Chemical Co., Ltd.) Sodium sulfite N,N-bis(sulfoethyl)hydroxylamine N-ethyl-N- (β- methanesulfonamidoethyl) -3-methyl-≠ 0.3g 0.3g /2. Og,g,tg O,03g 27.0g/ko,0g 27. 0g/, Og3. 0g 0.1g 0.1g 10, Og /j, Og - Add aminoanilino water 10100O1000m100O
,2j'C) 10.10 // , /.

Water 00ml Ammonium thiosulfate (7oog/l) 10oml Ammonium sulfite ≠Og Iron (III) ammonium ethylenediaminetetraacetate! ! g Ethylenediaminetetraacetic acid 5g Ammonium bromide ≠Og Nitric acid (A7%) Sog Add water 1000ml p100O'C) (with acetic acid and aqueous ammonia) z, r 130ml 230ml 00g 133g /+2. ! g 73g 73g 000ml j, t Rinse liquid (common to tank liquid and replenisher liquid) Ion exchange water (calcium, magnesium 2 ppm or less) The color obtained above was exposed to 1% sample & 20%, and subjected to the following processing step. Continuous processing was performed. Processing was continued until twice the capacity of the color development tank was refilled.

Also, sample flatness 20/~20! through an optical wedge to the rt
ocMs exposure was given and processing was performed before and after continuous processing.

Color development 3ri0Car seconds 70rnl 20
1 Bleach fix 3!0C hiroj seconds Aoml**201 rinse■ 3r"cso seconds ionsu7s■ 31
0C20 seconds 101j rinse ■ 3s'c
2o seconds 360rnil 1073dry r
o0c60 seconds (*photosensitive material/replenishment amount per m2) (rinse→
(3-tank countercurrent system to
In addition, 120 m per m2 of photosensitive material from rinse ■
In the photographic performance before and after continuous processing obtained above (1 liter was poured), the amount of change in Dtion is set as △Dmin, and
The amount of increase in dirt J was evaluated. Furthermore, the sample after the ΔDmin evaluation was washed for 1 minute with a 300 C cothiacetic acid aqueous solution. The change in D min before and after washing was evaluated.

The results are shown in Table 3.

As is clear from Table 3, if there is no water-soluble polymer having an amide bond, D m
It can be seen that i n increases and D min decreases with the acetic acid aqueous solution. In other words, it can be seen that the photosensitive material is heavily contaminated.

On the other hand, it can be seen that when a water-soluble polymer having an amide bond is present, good performance with less contamination can be obtained as long as the structure of the present invention is followed.

(Example-≠) In Experiment A10 of Example-/, the following compounds were changed and treated and evaluated in the same manner.

N,N-diethylhydroxylamine in the color developer ■Preservatives mentioned in the text (2) ■Preservatives mentioned in the text (3) ■Preservatives mentioned in the text (Ri) ■ Preservatives listed in the text (/3) ■ Preservatives listed in the text (l≠) were changed and evaluated, and similarly good results were obtained, but FiN, Many of them were relatively better than N-diethylhydroxylamine.

(Example-j) In Experiment 10 of Example-/, the following compounds were changed and treated and evaluated in the same manner.

/-Hydroxyethylidene-/,/- in color developer
Similar good results were obtained when 1) the compound described in the text (E-I-λ) and 2) the compound described in the text (E-I-7) were used instead of diphosphonic acid.

However, when no compound was used in place of /-hydroxyethylidene-/,/-diphosphonic acid, the treated stain increased by 0.02 in Dmin, and the filtration test also gave a bad rating. However, in the comparison of Experiment sr of Example 2, almost no change was observed even when the above compound was not used. Therefore, in the structure of the present invention, it has been found that compounds such as /-hydroxyethylidene-/ and /-diphosphonic acid give more favorable results.

(Effect of the invention) The method of the present invention reduces the generation of tar in the color developing bath.
Contamination of photosensitive materials due to coloring of the liquid can be significantly suppressed.

Claims (1)

[Claims] (1) In a processing method for color developing a silver halide color photographic light-sensitive material, the silver halide color photographic light-sensitive material substantially contains a substance represented by the following general formula [A], [B] or [C] containing a dispersion of lipophilic coupler particles made of at least one high-boiling organic solvent that is immiscible with water, the color developer containing at least one water-soluble polymer containing a repeating unit having an amide bond; and the sulfite ion concentration is 8x per liter of the above color developer.
1. A method for processing a silver halide color photographic material, characterized in that it contains 10^-^3 moles or less and substantially does not contain benzyl alcohol. General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (B) W_1-COOW_2 General formula (C) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, W_1, W_2, and W_3 may be the same or different. each of which may represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group).