JPS62275257A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To remarkably reduce environmental pollution control load, to relieve solution preparation work, and to prevent deterioration of density due to a cyan dye to be left in a state of leuco-compound by processing a silver halide color photographic sensitive material with a specified color developing solution containing substantially no benzyl alcohol within a specified developing time. CONSTITUTION:The silver halide color photographic sensitive material provided on a reflective support with at least one of the silver halide emulsion layer is imagewise exposed, and color developed with the color developing solution containing substantially no benzyl alcohol but <=1.5X10<-2>mol/l sulfite and <=1.5X10<-2>mol/l hydroxylamine within a developing time of 2min30sec. Said photosensitive material contains a magenta coupler represented by formula I in which Rb is H or a substituent; Y1 is a group to be released by the coupling reaction with the oxidation product of an aromatic primary amine color developing agent; and each of Za-Zc is optionally substituted methine, =N-, or -NH-.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a processing method for silver halide color photographic materials, and relates to a processing method which does not use patented benzyl alcohol and which significantly shortens color development time. .

(Conventional technology) In order to improve the color development of color photographic materials,
Various developing agent penetrants have been studied, and in particular, the method of adding benzyl alcohol to a color developer to speed up color development is currently being used in the processing of color photographic materials, especially color developers, due to its great color development promotion effect. widely used.

However, when a color developer containing benzyl alcohol is used, staining tends to occur, and to suppress this, preservatives such as hydroxylamine salts and sulfites are generally added to /l and 0.02
~0. It is effective to use θ damol/l. It has not been possible to reduce the amounts added below these amounts because the problem of significant staining occurs.

In addition, when benzyl alcohol is used, diethylene glycol, triethylene glycol, alkanolamine, etc. are required as solvents due to its low water solubility. However, these compounds, including benzyl alcohol, have low pollution load values. Since some BOD and COD are high, it is preferable to remove benzyl alcohol for the purpose of reducing pollution load.

Furthermore, even if this solvent is used, it takes time to dissolve benzyl alcohol, so it is better not to use benzyl alcohol, also for the purpose of reducing the number of 11 kg of paper milling work.

Furthermore, if benzyl alcohol is brought into the postbaking bath or bleach-fixing bath, it causes the formation of leuco dye of cyan dye, which causes a decrease in color density. Furthermore, since the washing-out speed of the developer components is delayed, the image storage stability of the photosensitive material may be adversely affected.

Therefore, also for the above reasons, it is preferable not to use benzyl alcohol.

Conventionally, color development was generally processed in 3 to 3 minutes, but with the recent shortening of finishing delivery times and the reduction of laboratory work, there is a desire to shorten the processing time. Ta.

However, if benzyl alcohol, which is a color development accelerator, is removed and the development time is shortened, it is inevitable that the color density will be significantly reduced.

(Problem to be Solved by the Invention) In order to solve this problem, various color development accelerators (for example, U.S. Pat. No. 29!θ970, -it/!/4t
No. 7, same, geta 2.903, same 2゜30g, 925
Issue, same q, 03♂, 07! No., same number, //9. Dub No. 2, British patent/, Gu! ! lg/No. 3, Tokukai Akira! 3-/! 7
3/issue, same j! -Otsu2gu! θ, same! ! - Otsu λ4t! /
Same issue! ! -Otsu 2nd verse- No., same! ! −≦2 da! No. 3, same!
? -! θ! 3rd issue, same ≦0-/422! No. Tokko Akira!
/-/Oichi No. 2, same! ! Even when K was used in combination with the compound described in No. 922 No. 922, sufficient color density could not be obtained.

Also, there is a method of incorporating a color developing agent (for example, a US patent!
, 7/9, 4t9λ issue, same 3, 34t2, j! 9
No. 3,392. ! No. 97, Tokukai Sho! g-≦23! Same issue! Otsu-/ni No. 733, same! 7-97! No. 37, same!
7-♂3! Otsu! Even if the method described in No. 1, etc. is used, it is not an appropriate method because it has the drawbacks that color development is delayed and fog is generated.

Also, a method using a silver chloride emulsion (for example, Japanese Patent Application Laid-Open No. 3-1998-
No. 233146, No. 2323≠2, No. 1,0-
The method described in No. 91, No. 0, etc.) is not a practically appropriate method due to high fog, and color development is significantly inhibited in the presence of sulfite ions.

As described above, no method has been found for obtaining color images with sufficient color development and less staining in a short period of time using a color developer that does not substantially contain benzyl alcohol. .

On the other hand, a method for promoting color development by incorporating an l-phenyl-3-pyrazolidone derivative into a silver halide color photographic light-sensitive material is disclosed in JP-A No. 7-7≠4Lj-da No. 7, JP-A No. 60-7≠ No. 4236, No. 61-30! No. 32, No. 4236, No. 61-30! I-//! No. 1A3r, 60-/! lll-111
7, tO-/Jrll'Ar, and 40-/6
Jr6! r/ issue etc. In addition, as a method for reducing benzyl alcohol concentration, JP-A-Sho! T-60!
No. 36 and JP-A-60-/JLR Hirohiro No. 6.

However, none of the patents specifically describes improvements in photographic properties under the conditions that the color developer substantially contains benzyl alcohol and the color development time is shortened to 2 minutes and 30 seconds or less. .

Therefore, an object of the present invention is to provide a processing method that substantially does not contain benzyl alcohol, provides sufficient color development even in a short processing time of 2 minutes and 30 seconds or less, and has less staining. It's about doing.

(Means for Solving the Problems) As a result of various studies, the present inventors have developed a silver halide color photographic light-sensitive material having at least one silver halide color photographic emulsion layer on a reflective support. , substantially free of benzyl alcohol, with a sulfite concentration of 7 g/l
or less, and the concentration of hydroxylamine salts is 2g
It has been found that the above object can be effectively achieved by carrying out a color development treatment in a time of 2 minutes and 30 seconds or less using a color developer having a concentration of 1.5% or less. Furthermore, with conventional color developers, problems such as staining occur when sulfites and hydroxylamines are reduced, but surprisingly, a color developer that does not substantially contain benzyl alcohol can be used for short processing times. It has been found that sufficient color density can be obtained without increasing the stain.

In particular, these effects were found in light-sensitive materials containing a magenta coupler represented by the general formula (+), which will be described in detail later.

The color developer used in the present invention does not substantially contain benzyl alcohol. "Substantially not containing" preferably contains no more than rml/l, more preferably 0.3ml
/l or less, and most preferably no benzyl alcohol at all.

Further, the color development time is 2 minutes and 30 seconds or less, preferably 30 seconds to 2 minutes. "Color development time" referred to here
refers to the time from when the photosensitive material comes into contact with the color developer until it comes into contact with the processing solution of the next bath.

Specific examples of sulfites used in the present invention include sulfite nose, potassium sulfite, lithium sulfite, bisulfite nose, potassium bisulfite, cal/rum sulfite, magnesium sulfite, strontium sulfite, and the like. However, the present invention is not limited to these compounds. Moreover, these sulfites may be added to the developer alone or in combination of two or more. The amount of the sulfite added to the color developer is ♂×10-3
mol/l or less, preferably /, Q×IQ 3~
t, rxiθ-3 mol/l.

Although the hydroxylamines used in the present invention can be used in the form of free amines in color developers, they are generally used in the form of water-soluble acid salts. Common examples of such salts are sulfates,
These include chloride, oxalate, phosphate, carbonate, acetate, and others. Hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of hydroxylamines may be substituted or unsubstituted.
It may be substituted with a J group and/or a hydroquine group.

These hydroquinyl aminos may be added alone to the color developer, or two or more thereof may be added in combination.

The amount of the hydroquinruamino compound added to the color developer is /
,! ×10 2 mol/! or less, preferably θ~3
．． ♂×/θ−3 moles/! It is.

Next, the magenta coupler represented by general formula (1) will be explained.

General formula (1) (In the formula, Rb represents a hydrogen atom or a substituent, Yl represents a group that can be separated by a coupling reaction with an oxidized aromatic seventh-class amine developing agent, and Z alzb or Zc is Represents a methine group, a substituted methine group, =N- or -NH-,
One of the Za-Zb bond and the zb-Zc bond is a double bond, and the other is a single bond. ) Details of the magenta coupler represented by general formula (1) will be explained below.

In the general formula [1], Rb represents a hydrogen atom or a substituent, and Yl represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Za, Zb and Z'c are methine, substituted methine,
=N- or -NH-, and the Za-Zb bond and Zb
One of the -Zc bonds is a double bond, and the other is a single bond.

The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, it also includes the case where a dimer or more multimer is formed with Rb or Yl. Also Za, Zb
Alternatively, when Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is also included.

In the general formula CI'3, the term "multimer" means one having two or more groups represented by the general formula [I] in the molecule, and includes bis-forms and polymer couplers.

Here, the polymer coupler is a tetramer having a moiety represented by the general formula 1) (preferably one having a vinyl group),
A homopolymer consisting only of vinyl monomer (hereinafter referred to as vinyl monomer) may be used, or a copolymer may be prepared together with a non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic-grade amine developer.

What is the compound represented by the general formula CI'll? Member ring-! It is a membered ring condensed nitrogen heterocyclic coupler, and its chromogenic nucleus exhibits isoelectronic aromaticity with naphthalene, and has a chemical structure that is generally referred to as azabontalene. General formula [■
] Preferred compounds among couplers represented by /H
-imidazo(/, 2-b)pyrazoles, /H-pyrazolo(/, r-b)pyrazoles, /H-pyrazolo[r
, /-c) [/, 2,4t] triazoles, /H-pyrazolo [/, t-b) [/,,! , 4t] triazoles, /H-pyrazolo[/, s-d]tetrazoles, and /H-pyrazolo[/, ra)benzimidazoles, each with the general formula cn]CI[I) CIV)[■
] Among these compounds represented by [■] and [■], particularly preferred compounds are [■] and [V].

([][:DI) c6 [■] [■] [■] Substituents R5, R6 and R7 of general formulas [■] to [■]
is a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
Heterocyclic group, cyano group, alkoxy group, aryloxy group, Hege X: 1-ring oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group,
Acylamino group, anilino group, ureido group, imide group,
Sulfamoylamino group, carbamoylated amino group, purkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group , represents a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and Yl is a hydrogen atom, a halogen atom, a carboxy group, or a group that is bonded to the carbon at the coupling position via an oxygen atom, nitrogen atom, or sulfur atom. Represents a leaving group.

R5, R6, R7-! Also included are cases where Yl becomes a divalent group and forms a bis body. Also, the general formula [■] ~ [
When the moiety represented by [■] is present in the vinyl monomer, R5, R6 or R7 represents a simple bond or a connecting group, and the moiety represented by the general formulas [H] to [■] is connected through this. and the vinyl group are bonded.

More specifically, R5, R6 and R7 are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, propyl group, t-butyl group,
Trifluoromethyl group, tridecyl group, 3-(2,it
-di-t-amyl7eth/xy)-1''ohill group, -1dodecylokinoethyl group, 3-phenoquinepropyl group, 2
-hex//lsulfonyl-ethyl group, chloro butyl group, pen/zyl group, etc.), aryl group (e.g., phenyl group, g- to -butylphenyl aLr, <t-di-t-amylphenyl group, y-tetradecanamidophenyl group, etc.), hetecI ring group (e.g.
7 groups, two-methoxyethoxy group, 2-dodecyloxy/nidoxy group, -1-meta/sulfonylethoxy group
W), acyloxy, G (e.g., phenoxy/group, dimethylphenoxy E=, "-t-butylphenoxy group,
etc.), heterooxy groups (e.g., 2-benzimidazolyloxy groups, etc.), acyloxy groups (e.g., acetoxy groups, hexadecanoyloxy groups, etc.), carbamoyloxy groups (e.g., N-phenyl-rubamoyloxy groups, etc.), 7'J5, N-ethylcarbamoyloxy 7 groups, etc.),
Silyloxy group (e.g. trimethylsilyloxy group,
etc.), sulfonyloxy groups (e.g., dodenosulfonyloxy, etc.), anrulamino groups (e.g., acetamido group, benzamide group, tetradecanamide group, α-
(2゜q-diamylfuninoquine)butyramide group, γ-(3-4-butyruderhydroxy/funinoxy)butyramide group, α-(g-(4t-humanmixyphenylsulfonyl)phenoxyl f7'7amide) groups, etc.), anilino groups (e.g., phenylamino group, euchloroanilino group, cochloro!-tetradecanamidoanilino group, 2-chloro-!-dodecyloxine group, anilino group, N-acetylanilino group, 2-chloroanilino group, -!-(α-(3-t-phthyl-q-hydroxy7phenoquine)dodeca/amide)anilino group, etc.), ureido group (e.g., phenylureido group, methylureido group,
N, N dibutylureido group, etc.), imide group (e.g., N-sulfonamide group, 3-be/zylhydantoynyl group, <t-(2-ethylhexanoylamino)phthalimide group, etc.), sulfonamide group, etc. famoylamino group (e.g., N,
°N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (e.g. methylthio group, octylthio group, tetradecylthio group, diphenoxyethylthio group, 3 -phenoxypropylthio group, 3-(/1t-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, 2-butoxy-t-t-octylphenylthio group, 3-butylphenyl thio group,
eucarpoxyphenylthio group, q-butrabucanamidophenylthio group, etc.), heterocyclic thio group (e.g.
2-benzothiazolylthio group, etc.), alkoxycarbonylamino 7 group (e.g., methoxycarbonylamino group,
tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, u,4t-di-tert-butylphenoxycarbonylamino group, mino group, !ri, sulfonamide group (e.g., Methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group,
(2-methyloxy-j-t-butylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl group, N,N-dibutylcarbamoyl M, N-
(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-(j-(2,
it-di-tert-7-milphenoxy)furoyl)carbamoyl group, etc.), decyl:X5 (e.g., acetyl group, (-2,
acetyl group, benzoyl group, etc.), sulfamoyl group (
Examples include N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N-(u-dodecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N- diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octadecyl (honyl group, benzenesulfonyl group, toluenesulfonyl i, L), sulfinyl 1 (flLtff,
octanesulfinyl group, dobufursulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group ( Examples Eva, phenyloxycarbonyl group, 3-pentadecyloxy-
carbonyl group, etc.), and X represents a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom, etc.),
A carboxyl group or a group linked with an oxygen atom (e.g., acetoxy group, fropanoyloxy group, benzoyloxy group, 2.4t-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, bilbinyl oxine group, cinnamoyloxy group, phenoxy group) , coucyanophenoxy group, goomethanesulfonamidophenoxy group, coumethanesulfonylphenoxy group, α~naphthoki7 group, J-
Hantadecylkenoxy group, pen/zyloxycarbonyloxy group, ethyloxy group, -monocyanoethoxy group, benzyloxy group, λ-7enethyloxy group, two-phenoxyethoxy group,! -phenyltetrazolyloxy group, λ-
7 benzothiazolyloyl groups, etc.), connected through nitrogen atoms! (For example, t, benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, co, 3.'l,!, b-hantafluoropenzamide group, octane sulfonamide group, p- Cyanophenylureido group, N,N-diethylsulfamoylamino group, /-pyrazolyl group, !,!-dimethyl-2.gudioxo-3-oxazolidinyl group, /-benzyl-ethoxy-3-hyda/toynyl group, 5N- 7,/-dioquine~J(,!H)-oxo-7,2-benzisothiazolyl group, 2-oquine/, 2-dihydro/-pyridinyl group, imidazolyl group, pyrazolyl group, 3,!-diethyl group/ , 2.gutriazol-/-yl, !- or 6
-promobenzotriazol-/-yl,! -Methyl-/, 2.3. Dartriazol-7-yl group, benzimidazolyl group, 3-benzyl-/-fold/toynyl group, /-benzyl-! -hexadecyloxy-3-hydantoynyl group,! -methyl-7-tetrazolyl group, goomethoxyphenylazo group, goupivaloylaminophenylazo group, two-hydroxy-goopropanoylphenylazo group, etc.), groups linked by a sulfur atom (e.g., phenylthio group, twocarpoxy Phenylthio group, twomethoxy J'-t-octylphenylthio group, g-methanesulfonylphenylthio group, co-octanesulfonamidophenylthio group, 2-butoxyphenylthio M, -z-
(+2-hexanesulfonylethyl)-s-tert-
Octylphenylthio group, benzylthio group, --cyanoethylthio group, /-ethquinalponyltritecylthio group,! - Phenyl j, j, g.

! -tetrazolylthio group, 2-benzothiazolylthio group, codedecylthio-! -thiophenylthio group, two-phenyl-3-dodecyl-/, 2.4t-triazolyl-
! -thio group, etc.).

When R5, R61, R7 or Yl becomes a divalent group to form a bis body, this divalent group can be described in more detail as a substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, / , 10-decylene group, -CH2C
H2-O-CH2CH2-1, etc.), a substituted or unsubstituted phenylene group (for example, /.

9-Phenylene tg, /,! -722lene group, -NHC
O-R5-CONH- group (Rs represents a substituted or unsubstituted alkylene group or phenylene group).

When those represented by general formulas (n) to [■] are present in the vinyl monomer, the linking group represented by R5, R6 or R7 is an alkylene group (substituted or unsubstituted alkylene group, for example, Methylene group, ethylene group, /, 10-decylene group, -CH2CH20CH2CH2-1, etc.), phenylene group (substituted or unsubstituted phenylene group, such as /, cuphenylene group, /, j-phenylene group, -CONH-
It includes groups formed by combining groups selected from 1-〇-1-〇CO- and aralkylene groups (for example, etc.).

In addition, the vinyl group in the vinyl monomer has the general formula [■] ~
It also includes cases where it has substituents other than those represented by [■]. Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 7 to q carbon atoms.

Acrylic acid, α
- Chloroacrylic acid, α-alacrylic acid (for example, methacrylic acid, etc.) and esters or amides derived from these acrylic acids (for example, acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, shi-butyl acrylate, 15O-butyl acrylate;
ethylhexyl acrylate), n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy/methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate)
, acrylonitrile, methacrylaterile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. , (vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N-vinyl-
Examples include λ-pyrrolidone, N-vinylpyridine, and two- and gouvinylpyridine. It also includes cases in which more than one of the non-color-forming ethylenically unsaturated monomers used herein are used together.

Compound examples and synthesis methods of couplers represented by the general formulas [■] to [■] above are described in the documents listed below.

The compound of general formula [■] is JP-A-Sho t'i'-/65 di-4
The compound of the general formula [I[1] is
-≠36, etc., the compound of general formula [IV] is the compound of Tokko Sho≠7-. 2'7L// etc., the compound of general formula [■] is
Tokukai Shojter/7/ri! 6 and same 10-/72ri 12
etc., the compound of general formula [■] is
λ, etc., and the compound of general formula [■] is described in US Patent 3.
oti, a32, etc., respectively.

Also, Tokukai Shojr-≠Ko Hiro, Tokukai Shojter 2/≠za! ≠, same jter/77! 3, same jter/77! The highly color-forming ballast group described in J.Hiroshi and J.T./77!17 is applicable to any of the compounds of the above general formulas [■] to [■].

Specific examples of the pyrazoloazole thread coupler used in the present invention are shown below, but the invention is not limited thereto.

+M-/1 tM-, 21 tM-j) (M-Hiroshi) (M-11 n CIOH21 (ClOH 21(;6Hx 3) (M-/Jl (M-7μ) FM-/j+ CH3n-(:sHt 3 (M-/A 1 (M-/71 CM-/J'1 rr-C6H13 +M-/?) (M-20) (M-ko/) shih3 1M-, 2λ) (M-13) +M- -da) α ShiH3 (M-rj) +M-,241 ShiaH17(t) (M-λ, r) H3 (M-λri) (M-jO1 n-(″10H21 CH3 CH3 H3 (M-60 ) CH3 (M-5,21 +M-j/1 (M-r31 0C4H9 CsHt7 (tl C8H17ft) Nl-1302UH3 (M-j/1 (M-11) (M-6≠) x:y=≠0: 10 x:y=jO:j+ri (weight ratio, same below) M-Ajl x:y=!0:10 (M-441 x:y=yoyo:≠! x: v=!0:60 These The coupler is generally added in an amount of 1.times.10@-3 to r.times.io" moles, preferably /.times.10" to z.times.io' moles per mole of silver in the emulsion layer.

In order to satisfy the characteristics required for a photosensitive material, two or more types of couplers etc. can be used together in the same layer, or the same compound can be added to 12 or more different layers.
Of course it doesn't matter.

To introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutylphthalate, dioctyl phthalate, etc.)
, phosphoric acid esters (diphenyl phosphate, triphenyl heptophosphate, tricresyl phosphate,
dioctylbutyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate) ), trimesic acid esters (e.g. tributyl trimesate), etc., or boiling points of 1o0C to/yo0C
After dissolving in an organic solvent such as lower argyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methylinobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., the hydrophilic colloid is prepared. distributed to The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Next, the color developer used in the present invention will be explained.

The color developer used in the present invention does not substantially contain benzyl alcohol. "Substantially not containing" means 0. The benzyl alcohol concentration is below rml/l,
Preferably, it does not contain any benzyl alcohol.

In the color developer of the present invention, in addition to a sulfite salt and a hydroxylamine salt, one type of preservative can be added as required.

For example, Tokukai Akira! --', t9r2r issue, same! 6-g7
θ3r, same! Core-3/g0, same! 9-/40/4
Aromatic polyhydroxy compound described in No. t2 and U.S. Patent No. 3.7 Gugo, O0; U.S. Patent 3, Otsu/J-, J-03
No. and British Patent/, jOA.

/Hydroxyacetones described in No. 7; JP-A-Sho! λ-/
4t302D issue and the same! 3-! Ri4t2! α- stated in the issue
Aminocarbonyl compound: JP-A-52-4t<</4t
J' and j7-! Various metals described in 374t No. 9, etc.: Various saccharides described in JP-A-627102727; same!
Hydroxamic acids described in No. 2-27≦3r; same! Tar/
α described in issue 60/41/.

α′-dicarbonyl compound; same! 9-/♂0! ? ! Symbol + Mosquito salicylic acids are the same! Alkanolamines described in Na-3ryo No. 32; same! Poly(alkyleneimine) described in Goichi Taku No. 399; same! Examples include gluconic acid derivatives described in Otsu-ZJl & No. 7. Two or more of these preservatives may be used in combination, if necessary.

The color developer used in the present invention can contain various aromatic grade amine color developing agents. Preferred examples are p-phenylenediamine derivatives, and representative examples are shown below, but the invention is not limited thereto.

D-/N, N-diethyl-p-7 22-diamine D-22-amino-! -ethylaminotoluene D-32-Amino-β-(N-ethyl-N-laurylamino)toluene D-<t Gu[N-ethyl-N-(β-hydrocoxy/ethyl)aminecoaniline D-rr -Methyl-9-[N-ethyl-N=(β- and droxyethyl)aminecoaniline D-, <N-ethyl-N-(β-methanesulponamidoethyl)-3-methyl-9-aminoaniline D -7N-(w-amine-y-diethylaminephenylethyl)methanesulfonamide D-I N,N-dimethyl-p-phenylenediamine D-ta (-amino-3-methyl-N-ethyl N-methoxyethylaniline D -/θ Guamino-!-methyl-N-ethyl-N-
β-Ethoxyethylaniline D-// Guamino-3-methyl-N-ethyl-N-
β-phthogyethylaniline These p-7 unilene diamine derivatives may also be salts such as sulfates, danates, sulfites, P-)luenesulfonates, and the like. The amount of the aromatic-grade amine developing agent to be used is from about 0.7 g to about 20 g per liter of solution, and more preferably about 0.0 g per liter of solution. ! g to about /θg.

In the present invention, among the above-mentioned color developing agents, compounds of D-4 are most preferred in terms of color development, hue, and image stability.

The color developer used in the present invention preferably has a pH of
The color developer has wa~/ko, more preferably wa~//, 0, and the color developer may contain other known developer component compounds.

For example, as the alkaline agent and pH buffering agent, caustic soda, caustic potash, soda carbonate, potassium carbonate, tertiary sodium phosphate, tertiary potassium phosphate, metaboric acid, borax, etc. can be used alone or in combination.

In addition, for the purpose of providing buffering capacity, for formulation convenience, or to increase ionic strength, it may be added to Various salt layers are used, such as alkali nitrate, alkali sulfate, etc.

In addition, various rice chelating agents can be used in the color developer to prevent precipitation of calcium and magnesium. Examples include polyphosphates, aminopolycarboxylic acids, phosphonocarboxylic acids, aminopolyphosphonic acids, /-hydroxyalkylidene/, /-diphospho/acids, and the like.

Any development accelerator can be added to the color developer if necessary. For example, various birimidium compounds represented by U.S. Pat. cationic dyes, neutral salts such as thallium nitrate and potassium nitrate, Japanese Patent Publication No. 11-30'1, US Patent J, 673.
No. 990, same.

! No. 31,732, same =, 9o 0.970, same 2, J
-77,127, nonionic compounds such as polyethylene glycol, its derivatives, and polythioethers,
US patent! , 20/, 2172 may be used.

In the present invention, an arbitrary amount of anti-capri agent can be added to the color developer if necessary. As antifoggants, alkali metal halides such as potassium bromide, sodium bromide, potassium iodide, and organic antifoggants can be used.

Examples of organic antifoggants include benzotriazole, gonitrope/zimidazole, and! -To Nitroiso Indazono! -Methylbenzotriazole,! - Nitropenzotriazole,! -Nitrogen-containing heterocyclic compounds such as rigorope/citriazole, corchiazolyl-benzimidazole, corchiazolylmethyl-benzimidazole, hydroxyazaindolizine, and/-phenyl-! - mercapto-substituted hetecX such as mercaptotetrazole, 2-mercaptopenzimidazole, 2-mercaptobenzothiazole! compounds, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid. Particularly preferred are nitrogen-containing heterocyclic compounds.

These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developer.

After color development, the silver halide color photosensitive material is usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment (bleaching and fixing) or may be carried out separately. Examples of bleaching agents include iron (ill), cobalt (1),
Compounds of polyvalent metals such as chromium (Vl) and copper (II),
Peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, M complexes of iron(I[) or cobalt(III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, /, 3-
Aminopolyphosphonic acids such as diaminopropanetetraacetic acid and cyclohexanediaminetetraacetic acid, or complex salts of M organic acids such as citric acid, tartaric acid, and phosphoric acid; persulfates, manganates, and nitrosophenols can be used. Among these, iron ethylenediaminetetraacetate ([11
) salt, diethylene) IJ amine iron pentaacetate (ml salt, 7
．． 3-diaminopropanetetraacetic acid iron(III) salt, cyclohexanediaminetetraacetic acid iron(III) salt, etc. are useful, and it is also effective to use them in combination.

Further, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution, if necessary. For example, in addition to bromide ion and iodide ion, U.S. Patent J, 70t, j≦/No., Special Publication Shogu J-F!
No. 03, No. q9-2311, Tokukai Sho! ! -327jJ
- No., same! 3-3g-33 and the same! Thiourea-based compounds as shown in 3-370It Specification tK, or JP-A-Sho! 3-/O 12gu No. 12, Dojo jj-9j Otsu No. 37, Dojo 3-17237, Dojo! 3-3273 No. Otsu, same! 3-t
ir732, same! Goo! No. 2J-34 and U.S. Pat. ♂93. J'! Thiol-based compounds as shown in Specification J, etc., or JP-A-4T? -J-96 Gugu issue, same! 0-/da No. 0729, same! No. J-2r'12, same No. 3-797623, same! 3-/θ9232,
same! Goo 3! Heterocyclic compounds described in R727 specification etc. or JP-A-Sho! Two 20♂32, same rs-s
so≦q, and jJ'-2,66θ, the thioether compound described in the specification, etc., or JP-A-Shogu? −
Quaternary amines described in the specification of ♂94t4tθ, or
Compounds such as thiocarbamoyls described in the specification of JP-A Sho <'9-', t2jltt No. 9 may also be used.

Examples of the fixing agent include thiosulfates, thionanates, thioether compounds, thioureas, and a large amount of iodides, but thiosulfates are generally used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing process and the fixing process, a washing process is usually performed. In the water washing process, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid to prevent precipitation, fungicides and anti-spiking agents to prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum salts. Typical hardeners, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Or L.E. West (L,
E, West), 'Water Quality
"Water Quality Crite"
ria), 7 Otographic Science and Engineering (Photo, Sci, andEng
, ), Volume 9, No. 3, (/9 Buri, etc.) may be added.Addition of chelating agents and anti-piping agents is particularly effective.In addition, multi-stage ( It is also possible to save water by adopting a countercurrent system (for example, from 2nd to 2nd).

In addition, after the water washing process
A multistage countercurrent stabilization treatment process as described in No. 7-trJ II No. 3 may be implemented. In the case of this process, λ~9
A tank countercurrent column is required. Various compounds are added to this stabilizing bath for the purpose of stabilizing the image.

For example, buffers for adjusting membrane pH (e.g. borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, carboxylic acids, etc.) and formalin. In addition, water softeners (
Inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), IN agent (
Proxel, inothiazolone, q-thiazolylbenzimidazole, halogenated phenol, etc.), surfactants,
A fluorescent brightener, a hardening agent, etc. may be added.

Moreover, various ring ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can be added as a simulated pH adjuster after the treatment.

In this treatment process, a constant finish can be obtained by preventing fluctuations in the liquid composition by using a replenisher for each treatment liquid during continuous treatment. The replenishment amount can be lowered to half or even less than half of the standard complement amount for cost reduction.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, etc., as necessary.

The silver halide emulsion used in the present invention is silver bromide, silver chlorobromide, or silver chloride that does not substantially contain silver iodide, and the silver halide preferably used contains 2 to 72 molt of silver chloride. Silver chlorobromide.

Here, "substantially no silver iodide" means that the silver halide does not contain silver iodide of less than λ molt, preferably not more than 1 molt, and more preferably does not contain silver iodide.

In silver chlorobromide, in order to obtain an emulsion with sufficient sensitivity without increasing the turnip IJi, it is preferable that the silver bromide content is 20 molar or more, but especially when rapidity is desired, the silver bromide content is preferably 20 molar or more. Below or i.

It may be preferable to use less than 100 ml. Reducing the silver bromide content not only improves the speed of development, but also reduces the amount of bromide ions accumulated in the developer when a photosensitive material containing it is run in a processing solution, and the developer itself It has high activity and is preferred for rapid processing.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure supporting a bonding structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or near-spherical particles, the particle size is defined as the particle diameter, and in the case of cubic particles, the particle size is defined as the ridge length, and the average particle size based on the projected area) is preferably λμ or less, o, or iμ or more, but particularly preferably Noha/μ or less 0. /jμ
That's all. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is 2.
So-called monodisperse silver halide emulsions with a width of 0% or less, particularly preferably 75% or less, are preferably used in the present invention.

In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably one with a variable rate) can be mixed in the same layer or coated in separate layers. Furthermore, one or more types of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), it may have an irregular crystal form such as a spherical shape, or it may have a composite form of these crystal forms. Tabular grains may also be used, and in particular, an emulsion in which tabular grains having a length/thickness ratio of 5 or more, particularly 5 or more, occupy 10% or more of the total projected area of the grains may be used. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface, or an internal layer image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography J" by Glafkides.

Chimie et Physique Photog
raphique (published by Paul Monte1, 79
g7)], by Duffin [Photographic Emulsion Chemistry J CG, F
, Photographic Emu by Duff in
lsion Chemistry (Focal Pre
ss, 79g6)], Zelikman et al., "Production and Coating of Photographic Emulsions J [V, L.

Making and by Zelikman et al.
Coating Potographic Emuls
In (Focal Press, /94g)]. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble silver salt may be one-sided mixing method, simultaneous mixing method, or a combination thereof. It's okay. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Furthermore, emulsions prepared by the so-called co-conversion method, which involves a process of converting silver halide already formed into silver halide with a smaller solubility product before the silver halide grain formation process is completed, and Emulsions which have been subjected to similar halogen conversion after the completion of the silver halide grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a talicum salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

After grain formation, silver halide emulsions are usually subjected to physical thermal acidification, desalting and chemical ripening before being used for coating.

Known silver halide solvents (e.g. ammonia, log/
Potash or U.S. Patent No. 3,27/, 767, JP-A-Sho
/-/23bu No. 0, Tokukai Akira! 3-t24t0♂, JP-A-53-/'141319, JP-A-JL-1007/
No. 7 or Tokukai Sho! Goo/! thioethers and thione compounds described in No. j/2♂ etc.) are precipitated, physically ripened,
Can be used in chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, methods such as Nudel water washing, 70 cure sedimentation method, or ultrafiltration method are used.

The silver halide emulsion used in the present invention contains active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfate,
Sulfur sensitization using thioureas, mercapto compounds, rhodanines)! -: Reduction-sensitized dimetallic compounds using reducing substances (e.g. stannous salts, amines, dorazine derivatives, formamidine sulfinic acid, 7rane compounds) (e.g. total complex salts, pt, Ir, Pd ,R
A noble metal sensitization method using complex salts of metals of group (1) of the periodic table such as h, Fe, etc. can be used alone or in combination.

Among the above chemical sensitizations, sulfur sensitization alone is more preferred.

- The back-sensitive, green-sensitive and red-sensitive emulsions of the present invention are spectrally sensitized with methine dyes and others so that they have color sensitivity. The dyes used include cyanine dyes,
Included are merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioquinol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A divalent color coupler substituted with a leaving group can reduce the amount of silver coated than a four-carrying color coupler in which the coupling active position is a hydrogen atom. Couplers in which the coloring dye has appropriate diffusivity, colorless couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected type anruacetamide coupler. A specific example is U.S. Patent No. 2.90
7. No. 210, No. λ, ♂2! , Of 7 and 3
．． 2bu! ,! It is described in No. 06 etc. The use of a two-wheel yellow coupler is preferred for the present invention, as described in U.S. Patent No. 3. gθ♂, /94 No. 3, <jg7.9ko♂ No. 3,933,601 and same No. 022
.

Oxygen atom separation type yellow coupler described in No. 62θ etc. or Tokuko Sho! No. ♂-10739, U.S. Patent No. 9. ltO/, No. 772, No. 32t, No. oaa, Research Disclosure (RD) /ror3
(Q/979), British Patent No. 1.4t2j, 02
No. 0, West German application publication cylinder =.

+2/ri, No. 912, No. 2. ,! t<7.347,
Same number! , 329. Typical examples thereof include the nitrogen atom separation type yellow couplers described in J♂ No. 7 and No. 4T33°R12. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. As the t-hi5so:y coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the coloring dye. 3//, No. 072, No. λ.

34tJ, 71!7J', same number, 600,7♂
? No. λ, 90? ,! No. 173, No. 3.0g, Otsu! No. 3, No. 3.7! It is described in λ, ♂9 No. Otsu and 3゜93, <, 0//, etc. Two pixels! The leaving group of the -pyrazolone coupler is preferably a diatomic leaving group as described in US Pat. No. q, 3/θ, No. 79 or an arylthio group as described in US Pat. Also, European Patent No. 73. tj≦
The pyrazolone couplers having a ballast group as described in No. 1 can provide a high degree of color development.

As a pyrazoloazole coupler, US Patent No. 3.
jj9. The pyrazolobenzimidazoles described in US Pat. , /-c) (/, 2.4t) Triazoles, Research° Disclosure -4t2λ
Pyrazolotetrazoles and Research Disclosure 211230 (
/? Examples include pyrazolopyrazoles described in ♂$1- (month). The imidazo[/,z-b)pyrazoles described in European Patent No. 1/9.74t/E are preferred from the viewpoint of low yellow side absorption of coloring dyes and light fastness, and European Patent No. 1/9. Pyrazolo [/] described in No. J'≦θ.

5-bl[/, 21g, j) Riazole is particularly preferred.

Among the above couplers, it is particularly preferable to use a pyrazoloazole coupler represented by the general formula (1).

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and are disclosed in US Patent No. 2,4t7g.

293, preferably the naphthol couplers described in U.S. Patent No. DA, 0! Ko, 2/K issue, same No. 9゜/gu Otsu, 39
No. 2, No. 2, +22/, No. 233 and No. 2
A typical example is the oxygen atom elimination type two-pixel naphthol coupler described in No. 9 Otsu, No. 200. Further, specific examples of phenolic couplers include U.S. Patent No. 2.3t9
, No. 929, No. 2. ♂0/, No. 171, No. λ, 7
72, /g- No. 2. It is written in the issue of ♂96.72. Humidity and temperature robust cyan couplers are preferably used in the present invention and are typically described in U.S. Pat. No. 3,772. 'oor, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus, US Patent No. 2.7
7,! , / Iko issue, same issue 3.7! r, No. 30/, No. g, /ko 3.39, No. 't, 3j'l, 0//, No. &, No. 327゜773, Hyakukyo Patent Publication No. 3.3
No. 29,729 and special request! ♂-'Co written in issue A247/etc.! - Diacylamine-substituted phenolic couplers and U.S. Pat. No. 3. &<1! d; ,42
No. 2, No. D, No. 333,999, No. G, 4tsi,
It has a funinylureido group at the λ-position and is described in rs9, a, g=7.7.67, etc. These include phenolic couplers having an anruamino group at the - position.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are disclosed in U.S. Patent No. 9.3≦B.

JJ No. 7 and British Patent No. 2. /2! , No. 670 contains a specific example of a magenta coupler, and European Patent No. 9 <, j7
No. 0 and Seibito Application Publication No. J', 2j'A.

No. 533 describes specific examples of yellow, magenta or uncoupler.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. ri6/, 72
No. 0 and No. 1, o, ro.

It is described in issue 2//. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. G, 332.2F.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more different layers using the same compound. It can also be introduced into

The coupler used in the present invention can be introduced into the light-sensitive material by an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is /
After dissolving either a high boiling point organic solvent of 7J-0C or higher and a low boiling point so-called auxiliary solvent alone or in a mixture of both, fine particles are dissolved in water or an aqueous medium such as an aqueous gelatin solution in the presence of a surfactant. Spread. Examples of high boiling point solvents are described in US Pat. No. 2,3,027, and the like. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high-boiling organic @ agents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (a)
Phenyl phosphate, tricresyl phosphate, diethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, driftoxyethyl phosphate, trichloropropyl phosphate,
ethylhexyl phenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate, dodecylpe/soate, -monoethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohol Qi4 tajaphenols ( instearyl alcohol, co-, tert-amylphenol), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl Examples include phthaltoxy (j-tert-octylaniline), hydrocarbons (grafine, dodecylbenzene, diimpropylnaphthalene, etc.). In addition, as an auxiliary solvent, the boiling point is about 3o0
C or higher, preferably! Organic solvents with a temperature of 0°C or more and about/40°C or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone,
Examples include cyclohexanone, two-ethoxy7-ethyl acetate, dimethylformamide, and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. j4t/.

Near < and No. 2. ! <No. 11,230 etc.: (
Are listed.

Typical usage amounts for color couplers range from 0.00/mol to 1 mol/mol of photosensitive silver halide, preferably from 0.0/mol to 0.0/mol for yellow couplers.
! 0.003 to 0.3 for mono to magenta couplers
moles, and for cyan couplers 06θ02 to 0.3
It is a mole.

The light-sensitive materials produced using the present invention can be used as color capritic or color mixing inhibitors such as hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfones, etc. It may also contain amidophenol derivatives and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic antifading agents include idouquinones, di-hydroquine chromans, r-hydroxycoumarans, spirochromans a, p'-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes,
Typical examples include amine phenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-,N,N-dialkyldithiocarbamado)nickel complex can also be used.

Prevents deterioration of yellow dye images due to heat, humidity and light Compounds having a hindered amine and hindered phenol image moiety structure in the same molecule, as described in U.S. Patent No. & J, 4/, J'93 gives good results. In order to prevent deterioration of agenta dye images, especially deterioration caused by light, spiroindanes described in JP-A-JJ-/J-94gg and JP-A-KAI! -! -J'9♂3-
Hydroquinone dietheno or monoether capped chromans described in the above issue give preferable results.

In order to improve the storage stability of the cyan surface image, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. The UV absorber may be co-emulsified with the 77 coupler.

The coating amount of the ultraviolet absorber may be sufficient as long as it imparts photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is usually preferably /X10-4 mol/m2 to 2X10-3 mol/m2, especially jXlo-4 mol/12 to/.

! It is set in the range of X10-3 mol/m2.

In the conventional light-sensitive material layer structure of color paper, two ultraviolet absorbers are contained in either layer on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The photosensitive material of the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer for various purposes such as anti-halation or halation prevention.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble brighteners may be used, and water-insoluble brighteners'
may also be used in the form of a dispersion.

The present invention, as described above, is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Further, each of the above-mentioned emulsion layers may be made up of more than one emulsion layer having different sensitivities, and a non-light-sensitive layer may be present between λ or more emulsion layers having the same sensitivity.

The light-sensitive material according to the present invention is preferably provided with supporting layers such as a /.C silver germide emulsion layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a bank layer.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein:
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives;
Various synthetic hydrophilic polymer substances such as mono- or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

In addition to lime-treated gelatin, acid-treated gelatin and 1 Journal of the Japanese Society of Photographic Science J (Bull, Soc, Sc.
i, Phot, Japan,) A/t, 3g
Enzyme-treated gelatin as described on page 9 (g) may be used, and hydrolysates and enzymatic decomposition products of gelatin may also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developers or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are listed in Research Disclosure (Res.
7 t tl
j (July-February 97t) and /177≦(/
It was written in 1997///month).

The reflective support J that can be 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, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. , baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent support with a reflective layer or a reflective material, such as glass plate, polyester film such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

〔Example/〕

Multilayer color photographic papers (1) to (2) having the layer configurations shown in Table A with different magenta couplers were prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (a)/9.7g and color image stabilizer (b)
)g, 4tg vinegar fix chill 27.2m/l and solvent (
c) 7.9 m/ml was added and dissolved, and this solution was emulsified and dispersed in rsml of a 10% aqueous gelatin solution containing 70% sodium dodecylbenzenesulfonate♂ml. On the other hand, a blue-sensitive sensitizing dye shown below was added to a silver chlorobromide emulsion (silver bromide 0 mo1%, containing Ag 70 g/kg) at silver chlorobromide/mO! Hit 7. 9 gg of a blue-sensitive emulsion was prepared by adding Ox/θ-4mall. The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table A to prepare a first layer coating solution.

The coating liquids for the λth layer to the seventh layer were also prepared in the same manner as the first layer coating liquid. The gelatin hardening agent for each layer is /-oxy-3,! -dichloros-) riazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

-1:Me(D-1 night-sensitive emulsion layer (CH2)45O3e(CH2)4SO3Na■ (7.θX per mol of silver halide/0-4 m
ol addition) Green-sensitive emulsion layer 5O3HN(C2H5)3 (4t, t per silver halide/mOl) X/0-
4 mal addition) S03HN(C2H5)3 (7.0X10 5 mol added per silver halide/mol) Red-sensitive emulsion layer C2H5'I eC2H5 (〇×/θ-4 mol added per silver halide/mOl) of each emulsion layer The following dye was used as the anti-irradiation dye.

Green-sensitive emulsion layer: Red-sensitive emulsion layer.

The structural formulas of the compounds used in this example, such as couplers, are as follows.

(a) Yellow coupler H3 (b) Color image stabilizer (C) Solvent (d) Color mixing prevention agent (e) Solvent The magenta couplers used are as follows.

Sample ■ (The amount of silver in the third layer was 0.jjf'/m2.

) Sample O Exemplified compound M-≠1 Sample @ Exemplified compound M-μ3 Sample ■ Exemplified compound M-z7 Using a light-sensitive needle (color temperature 32000K of FWH-ya light source manufactured by Fuji Photo Film ■), blue, Gradation exposure for centometric measurements was provided through green and red filters. The exposure at this time was 2jOCM with an exposure time of 0°5 seconds.
The exposure amount was set to S.

The above exposure source light-sensitive material was processed in the following processing steps.

(Processing process) (Temperature) (Time) Color development process 3j0C≠! Second bleaching constant tank process 3!0C Hiro! Second washing step 3!0C7 minutes 30 seconds Drying step 20601 minutes 00 seconds The treatment recipe used is as follows.

As for the color developer, formulation A containing benzyl alcohol and formulation B not containing benzyl alcohol were used.

(Color developer prescription) Prescriber Prescription B ethylenetriaminepentaacetic acid, Og 2.0g benzyl alcohol /j Go
-diethylene glycol lo tri -Na
2SOa Addition amount KBr listed in Table 1
O, 4g 0.6g hydroxylamine sulfate Addition amount listed in Table/≠-Amino-3
- Methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl')-p-phenylenediamine sulfate ≠, jg ≠, jg Add water 1000p / 000p pH 10, +2!
10. +2! (Bleach-fix solution formulation) Ammonium thiosulfate (j4!wt section) lyo0m1Na2
SO3/ 7g NH4 (Fe(III)tEDTA)) j!
gEDTA-2Na gWater was added to give a total volume of 1000 ml (1000 ml)) The maximum and minimum concentrations of the obtained magenta dye were measured using a Macbeth densitometer, and the results are shown in Table 1.

It can be seen that in comparison examples tA and U), the color density decreases when benzyl alcohol is not added.

Also, when benzyl alcohol is added (black 3゜j, G
, 7) It can be seen that fogging occurs.

On the other hand, it has been shown that when the appropriate amounts of Na2SO3 and hydroxylamine of the present invention are used, sufficient color development can be obtained with less fogging even without the use of benzyl alcohol.

Furthermore, it can be seen that when a magenta coupler represented by the general formula (11) is used, even better color development is exhibited (
Photosensitive materials (→～■).

〔Example! ]

In Example/, when the water washing was changed to the following rinsing bath and the following treatment steps were carried out in the same manner as in Example//, fogging was observed even without benzyl alcohol at the concentration of sodium sulfite and hydroxylamine of the present invention. sufficient color development was obtained.

Processing process Temperature Time Color development (Jj'C) Hiroj second bleach constant layer
(3yo'C) us seconds rinse/ (3t0c) 2o seconds rinse 2
(3r0C) 2o second rinse 3 (350C
) - Dry for 0 seconds (10oC)
60 seconds (rinsing liquid) /-Hydroxyethylidene- /,7'-diphosphonic acid (40 yen) 1.6 Bismuth gochloride 0.3jg Polyvinylpyrrolidone 0.26g Aqueous ammonia (λ
6chi) 2. ! ml nitrilotriacetic acid・j
Na 1. ogEDTA-pHo, j g sodium sulfite /, Ogyo-chloro-2-methyl-≠ -isothiazolin-3-one
! 0~Two octyl≠-inchazoline-3-one! Q η Fluorescent brightener (Hiroshi, Hiro'-diaminostilbene series) / Add Og water to 10100O potassium hydroxide
pH 7.5 (pH may be adjusted with hydrochloric acid) [Example 3] Color developer in Example 1 &/! ,! .

4.7. r, ri, 10. //, /2. /3. /It.

After putting each of /l't in a plastic container and leaving it for a month at ≠Q0C, we observed the color of each layer and the degree of tar generation, and found that benzyl alcohol tlNfruya/, 3. j,
ls, 7 generated tar despite the large amount of preservative, whereas the color developer of the present invention (Mu♂,?, 10.//, /ko, which does not contain benzyl alcohol)
/J, /Hiroshi.

/j), there are almost no tars and rues,
It was found that the liquid has excellent stability over time.

[Example≠]

A multilayer color photographic paper having the layer structure shown in Table B with different magenta couplers was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (a)/9, ig and color image stabilizer (
b) 27.2 ml of 4t, lltgK ethyl acetate and 7.9 ml of solvent (c) were added and dissolved, and this solution was diluted with 10% sodium chloride containing 10 ml of sodium tidodecylbenzenesulfonate.
It was emulsified and dispersed in gelatin aqueous solution/♂tmJ. On the other hand, silver chlorobromide emulsion (silver bromide /, Omo1%, 1g70g/kg
silver chlorbromide/mol of the sensitizing dye shown below
90 g of a blue-sensitive emulsion was prepared by adding 4 mol of F) f, 0X10. The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table 8 to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. The gelatin hardening agent for each layer is /-oxy-3,! -Dichloro-3-triazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

-m: clear; -one blue-sensitive emulsion layer (silver halide/motla lita, θx10 4mol
Addition) Green-sensitive emulsion layer (addition of θ x 704 mol per silver halide/rnol) (7.0 x 10 5 mol per silver halide/mol)
Addition) Red-sensitive emulsion layer C2H5IeC2H5 (silver halide / mol o, q X /
(Addition of 0-4 mol) The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer: Red-sensitive emulsion layer: The structural formulas of the compounds used in this example, such as couplers, are as follows.

(a) Yellow coupler H3 (b) Color image stabilizer (C) Solvent (d) Color mixing inhibitor (e) Solvent All examples of multilayer color photographic paper obtained as above -
It was treated using the same process. However, the amounts of benzyl alcohol, sodium sulfite, and hydroxylamine in the color developer were varied as shown in Table 2.

The processing solutions used are as follows.

Color developer triethanolamine 10 gN,
N-diethylhydroxylamine Hirog fluorescent whitening agent (+, Hiro'-diaminostilbene type) 3. og Benzyl Alcohol Table λ Sodium Sulfite
Table λ Hydroxylamine/Sulfate
Table 2 Potassium carbonate 30 g
EDTk-2Na-2H202g Potassium bromide 0.0/g≠-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-fuynylenediamine sulfate! , add Og water / 000rttlp Hi o
, 2゜Bleach-fix solution EDTkFe(m)NH4・2H2040gEDTA-
JNa-2HzOhiro g Ammonium thiosulfate (70%) lxornl Sodium sulfite / 6 g Acetaldehyde-sulfite adduct 10 g Glacial acetic acid
Add 7g water
l000vtlpHj,! Add rinsing solution EDTA-, 2Na-JH200, tAg water, tooml pH 7, OB, Dmin and Dmax for B, G, and R. Table 2v shows the following.

According to the present invention (Tsuta λl-23), sufficient color density can be obtained with little fog, but when benzyl alcohol is present (A/6), fog occurs, and hydroxylamine and sulfite are present. D if present at a concentration higher than the concentration of the invention
max decreases.

(A/7-20) (Effects of the present invention) By carrying out the present invention, benzyl alcohol can be substantially eliminated, thereby significantly reducing the pollution load, reducing liquid preparation work, and reducing cyan dye from the leuco form. It is possible to eliminate the decrease in concentration caused by staying at a certain temperature. In addition, even when the color developer is stored for a long time, no tar is generated and the storage stability is excellent.

Furthermore, a large amount of color printers can be processed quickly and productivity can be dramatically improved. Furthermore, according to the present invention, even when processing is performed for a short time with a color developer that does not substantially contain benzyl alcohol, there is little decrease in color density.
In addition, a good color image with low capri (stin) can be obtained.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural Amendment (Self-imposed January 1, 1986)

Claims (2)

[Claims] (1) After imagewise exposure of a silver halide color light-sensitive material having at least one silver halide emulsion layer on a reflective support, it contains substantially no benzyl alcohol and has a sulfite concentration of 8 x 10^-^. 3 mol/l or less, and the concentration of hydroxylamines is 1.5 x 10^-^2 mol/l
A method for processing a silver halide color light-sensitive material, characterized in that color development is carried out in a time of 2 minutes and 30 seconds or less using the following color developer. (2) A method for processing a silver halide color photographic material according to claim 1, wherein the silver halide color photographic material contains a magenta coupler of the following general formula (I). . General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. , Za, Zb or Zc represents a methine group, a substituted methine group, =N- or -NH-,
One of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. )