JPS62275260A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain sufficient color developing performance and to reduce fog through processing in a short time without adding substantially any benzyl alcohol by color developing 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 within a developing time of 2min30 sec with the color developing solution containing substantially no benzyl alcohol but one of the compounds represented by formula I and at least one selected from tetramethylammonium acetate, choline, hydroxyethylmorpholine, and the like. Said photosensitive material contains a magenta coupler represented by formula II. In formulae I and II, R<1> is 1-10C alkyl; each of R<2> and R<3> is H or the like; 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, or the like.

Description

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

[Conventional technology] In order to improve the color development of color photographic materials,
Various developing agent penetrants have been studied, and in particular, a method of adding dill alcohol to a color developer to speed up color development is currently used in color photographic materials, especially color knee/e- Widely used in the treatment of

However, when benzyl alcohol is used, diethylene glycol, triethylene glycol, or the like is required as a solvent due to its low water solubility. However, since these compounds, including benzyl alcohol, have a high BOD+COD, which is a pollution hazard and unloading, it is preferable to remove benzyl alcohol for the purpose of reducing the pollution load.

Furthermore, even if this solvent is used, it takes time for K to dissolve benzyl alcohol, so it is better not to use benzyl alcohol in order to reduce the preparation work.

Furthermore, if benzyl alcohol is brought into the bleaching bath or bleach-fixing bath, which is a post-bath, it causes the formation of a leuco dye, which is a cyan dye, and causes a decrease in color density. Furthermore, since the washing-out speed of the developer components is delayed, the image storage stability of the processed 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 30 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.

In order to solve this problem, various color development accelerators (for example, U.S. Pat.
, /lA7, same λ, ≠ 6. ri No. 03, same r, 301
A, No. 926, 4g, Dlr, 07! No., same≠,
//9. Hirot No. 2, British patent/.

≠30. Tata R issue, same/,≠yo! , ≠ / No. 3, JP-A-1
3-/jll / issue, 1j-421710, same!
! -tko≠j1, same! j-124su No. 2, same! j-6
No. 24113, No. 5r-ror3+, No. 60-/62
2j6, special public Shoj/-7.2≠λλ, same! ! −μ2
Even when used in combination with the compound described in No. 721, sufficient color density could not be obtained.

Also, method C incorporating a color developing agent, for example, U.S. Patent No. 3
,7/ri, ≠ Octopus, same J,! ≠2. j yo no. 2, yo no. 3.
3≠2. j5'7, Tokukai Shoj Otsu-423j, sameyoj
-14133, 7-ta 7, 31, Ro J-7-r
Even if the method described in No. JjAj etc. is used, it is not an appropriate method because it has drawbacks such as slow color development and formation of fog.

Also, method C using a silver chloride emulsion, for example, JP-A-Shoj1-
91J44j issue, same! Day No. 2323412, 40-
The method described in No. 11Ao, etc.) causes high fog and is not suitable for practical use.

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

Problems to be Solved by the Invention) Therefore, in the present invention, benzyl alcohol is not substantially contained, and even in a short color development time of 2 minutes and 30 seconds or less, there is little fog and sufficient The object of the present invention is to provide a processing method that provides color development.

Means for Solving All Problems C) The object of the present invention has been achieved by the method described below. That is, (11) A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support is substantially free of benzyl alcohol and is a compound represented by the following general formula II), Tetramethylammonium acetate, choline, choline chloride, hydantoic acid, allylamine, aminoguanidine sulfate, o-
Aminobenzoic acid, L-C+1-cysteine hydrochloride, benzylamine, DL-serine, morpholine, 0-
Processing of a silver halide color photographic light-sensitive material, characterized in that the processing is carried out in a color developer containing at least one component selected from aminobenzyl alcohol, quinuclidine, and hydroxyethylmorpholine for a time of 2 minutes and 30 seconds or less. Method.

(2) The method for processing a silver halide color photographic material according to (1) above, wherein the silver halide color photographic material contains a magenta coupler represented by the following general formula II [).

It was found that this can be effectively achieved.

General formula 111 (R' is an alkyl group having /~i'o carbon atoms, R2 and R3 are each a hydrogen atom, or 7 to
It is an alkyl group having 70 carbon atoms. ) General formula (■) In formula C, Rb represents a hydrogen species or a substituent group, Yl represents a group that is separated by a coupling reaction with an oxidized aromatic primary amine developing agent, and Za, zb or Zc represents a methine group, a substituted methine group, =N- or -NH-i, one of the Za-Zb bond and the zb-Zc bond is a double bond, and the other is a single bond. ) Next, general formula (I)K will be explained in detail.

General formula I■I R1 is an alkyl group having /~io carbon atoms, preferably an alkyl group having -~j carbon atoms. R2
and R3 are each a hydrogen atom or an alkyl group having 7 to 10 carbon atoms, preferably hydrogen'
Number of atoms or carbons/~! number of alkyl groups.

Specific examples of R1-R3 in the general formula fI> representing an alkyl group include a methyl group, an ethyl group, an i-propyl group, an n-hexyl group, a cyclohexyl group, a decyl group, and the like.

These alkyl groups may be substituted with a chlorine atom, carboxyl group, or alkoxy group.

The compound represented by the general formula (I) is an inorganic acid (e.g.
Hydrochloric acid, sulfuric acid, etc.) or an organic acid (eg, oxalic acid, acetic acid, I)-toluenesulfonic acid, etc.).

Specific examples of the compound represented by the general formula rI) are shown below, but are not limited to konera.

■-/ Trimethylamine ■-Co Diethylamine ■-J Methylamine ■-≠ Triethylamine ■-j Dipropylamine I-1 Diisopropylamine I-7 Ethylamine T-r Dimethylamine ■-T t-Aminohexanoic acid ■-10 Glycine ■ -///,/-aminoundeconic acid The above-mentioned compound and the (?) metal article described in claim (1) may be entirely in the form of a salt with various organic or inorganic acids.

The amount of these compounds added to the color developer is preferably 0.0/? -20? , more preferably 0. /ri~ioy.

Next, details of the magenta coupler represented by the general formula (It) will be explained.

In the general formula (n:l, Rb represents a hydrogen atom or a substituent, and Yl represents a hydrogen atom or an aromatic primary amine.
Represents a group that can be separated by a coupling reaction with an oxidized JR drug. Za, Zb and Zc represent methine, substituted methine, =N- or -NH-, and the Za-Zb bond and Z
One of the b-Zc bonds is a double bond and the other is a single bond.

When Z b -Z c is a carbon-carbon double bond, it includes the case where it is a part of an aromatic ring. Furthermore, FLb or Y
It also includes the case where a dimer or more multimer is formed with l. Also Z
When a, zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer.

General formula [■]: 2. Multimer means one having 1 = 2 or more groups of the general formula [■] in 7 molecules, and bis forms and polymer couplers are also included. include. Here, the polymer coupler may be a homopolymer consisting only of a monomer (preferably one having a vinyl group, hereinafter referred to as vinyl monomer) having a moiety represented by the general formula CIn), or it may be a homopolymer consisting only of a monomer having a moiety represented by the general formula CIn), or an aromatic-grade amine developed Copolymers may also be made with non-chromogenic ethylene-like monomers that do not couple with the cross-oxidation product.

What is the compound represented by the general formula (1[1)? It is a membered ring-membered ring fused nitrogen heterocyclic coupler, and its color-producing nucleus exhibits isoelectronic aromaticity with naphthalene.

Its chemical structure is commonly referred to as azapentalene. Preferred compounds among the couplers represented by the general formula C1[I] are /H-imidazol:/, 2-b]pyrazoles, /l(-pyrazolo[/,j-b]pyrazoles, /) l-pyrazolo [j,! -c) C/+21”
:]) Liazoles, / H-pyrazolo [1,! -bl
) c/, 2. K]) Riazoles, / H-pyrazolo (
'+s-a]tetrazoles and /H-pyrazolo[/,
r-a]benzimidazoles, respectively represented by the general formulas [:IVII:V]CVI)[■][■] and [■].Among these, particularly preferred compounds are CV
l] and [■].

[■]

Substituents R7, R8 and R9 of general formulas [■] to [■]
is a hydrogen atom, a halogen atom, or an alkyl group.

Aryl group, heterocyclic group, cyan group, alkoxy group, aryloxy group, heterocyclic oxy group, alkoxy group, carbamoyloxy group, nriluoquine group, sulfonyluoquine group, acylamino group, anilino group, ureido group, imido group, sulfonyloxy group famoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group,
Alcoquinecarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, Yl is a hydrogen atom, a halogen atom, Represents a carboxyne group, or a group that is bonded to carbon at the coupling position via an oxygen atom, nitrogen atom, or sulfur atom and is decoupled.

R7, R8, R9 or Yl is a divalent group.

This also includes cases where a screw body is formed. Also, the general formula CIV
] ~ The moiety represented by CIXI is in the vinyl monomer (
: In some cases, R7-R8 or R9 represents a mere bond or linking group, through which the general formula CIV) ~ [
(2) The moiety represented by ] and the vinyl group are bonded.

For more details, see rL7. R8 and R9 are hydrogen atoms,
・Rogon atoms (e.g. chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, J-(2,
t-di-t-amylphenoquine) propyl group, codedecyloxyethyl group.

3-phenoquinepropyl group, 2-hequinylsulfonyl-ethyl group, ncrobutyl group, hensyl group, etc.), aryl group (e.g., phenyl group, monobutylphenyl group, kotl-di-t- amyl phenyl group, V-tetradecanamidophenyl group, etc.), peterocyclic group (e.g. 2
-furyl group, niechenyl group, 2-pyrimidinyl group, 2
-benzothiazolyl group, etc.), cyano group, alkokyne group (e.g. methoxy group, ethkyne group, 2-methoxyethoxy group, 2-dodecyl olequinethoquine group, 2-methanesulfonylethoquine group 1, etc.), arylthio group (e.g. , phenoxy group, dimethylphenoxy group, g-t-butylphenoquine group, etc.), heterocyclic okyne group (e.g., 2-
benzimidazolyloxy group, etc.), acetoquine group (e.g., acetoquine group, hexadecanoyl oxine group, etc.)
.

Carbamoyloxy M (e.g., N-phenylcarbamoyloxy M + N-ethylcarbamoyloxygen 1, etc.)
, silyl-oquine group (e.g., trimethylsilyl-oquine group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamide group, benzamide group, tetradecanamide group, α
-(2°l-di-t-amylphenoquine)butyramide group.

γ-(3-1-butyl-g-hydroxyphenoxy)butyramide group, α-(g-(g-hydroxyphenylsulfonyl)phenoxy)decaneamide group, etc.), anilino group (e.g., phenylamino group, cochloroanisono group) , Coke coro-5-tetradecanamide anilino group,
Cochloro-! −(α−(
3-1-butyl-9-hydroquinphenoquine) dodecanamido) anilino group 1, etc.), ureido group (e.g., tert, phenylureido group, methylureido group, N, N dibutylureido group, etc.), imide groups (e.g., N-succinimide group, 3-penzylhydantoynyl group, -(,2
-ethylhexanoylamine) phthalimide group, etc.),
Sulfamoylamino group (e.g. =N, N-dipropylsulfamoylamino M, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (e.g.
Methylthio group, octylthio group, tetradecylthio group,
2-phenoxyethylthio group, 3-phenoxypropylthio group -J-(St-1-butylphenoquine)propylthio group, etc.), arylthio group (e.g., phenylthio group, niebutquine-r-t-octylphenylthio group, 3-Pentadecylphenylthio group% cocarpoquinphenylthio group, gutetradecanamidophenylthio group, etc.), heterocyclic thio group (e.g. copenzothiazolylthio group 1, etc.), alkoxycarbonylamino 2! (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloquine group (e.g., phenoxycarbonylamino group,
tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (for example, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group -p-), luenesulfonamide group, octadecanesulfonamide group. 2-methyloxy-tert-i-methylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl group%N
, N-dibutylcarbamoyl group, he(2-dodecyloxynethyl)carbamoyl group, N-methyl-hedodecylcarbamoyl group, N-13-(2,di-tert)
-amylphenoxy)propyl carbamoyl group, etc.)
.

Acyl group (e.g. acetyl group, (,2,ni-te)
rt-amylphenoxy)acetyl group, benzoyl group,
etc.), sulfamoyl group (e.g., N-ethylsulfamoyl group +N, N-dipropylsulfamoyl group -N-
(2-dodecyl quinethyl) sulfamoyl group, N-
Ethyl-N-dodecylsulfamoyl M, N, N-diethylsulfamoyl group, rg,)' Sulfonyl group (
For example, methanesulfonyl group, octanesulfonyl group,
benzenesulfonyl group, toluenesulfonyl group, etc.).

, ;t, /I/ 7 Inyl MC examples, t, octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl groups (e.g., t
For example, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group,
etc.), aryloxycarbonyl group (e.g., phenyloxinecarbonyl group, 3-intadenyloxycarbonyl group, etc.), and X represents a hydrogen atom, a halogen atom (
For example, a chlorine atom.

bromine atom, iodine atom, etc.), a carboxyl group, or a group connected by an oxygen atom (e.g., acetoquine group, propanoyloxy group, indiyloxy group, 21-dichlorobenzoyloxy group, ethoxyoxaloyloxy group,
Pyrvinyloxy group, cinnamoyloxy group, phenoxy group, l-cyanophenoquine group, l-methanesulfonamidophenoxy group, coumethanesulfonylphenoxy group, α-naphthoxy group, 3-pentadecylphenoquine group.

Benzyloxycarbonyloxy group, Etchin group.

-monocyanoethoxy group, penzyloquine group, 2-7enethyluoquine group, 1.2-phenoxyethoxy group, y-phenyltetrazolyluoquine &, 2-penzoteazolylluoquine group 1, etc.), groups connected via nitrogen atom (For example, benzenesulfonamide group, N -x tiltoluenesulfonamide group, heptafluorobutanamide group 1,2,3.L
lt, t, +-ba/tafluoropenzamide group, octane sulfonamide group, p-cyanobenylureido M,
NlN-diethylsulfamoylamino group, /-hiheridyl group,! ,! -dimethylco, l-dioquine-3-oxazolidinyl group, l-benzyl-ethquine-3-hydantoynyl group, 2N-/, /-dioxo-3(2H)-
Oxo-l, 2-benzisothiazolyl group, co-oxine-7. Cordihydro l-pyrinnyl group, imidazolyl group-pyrazolyl group, 3,! -diethyl/, 2. 'tt
-triazol-/-yl, j- or o-promobenzotriazol-l-yl, termethyl-/, 2. J
, '1-triazol-l-yl group, benzimidazolyl group, 3-benzyl-/-hydantoinyl &, /-benzyl-! -hexadecyloxy-3-hydantoinyl group-! -Methyl-/-tetrazolyl group.

l-methquinphenylazo group, 9t-pivaloylaminophenylazo group, 2-hydroxy-l-propanoylphenylazo group, etc.), groups linked by a sulfur atom (e.g. phenylthio group, 2-carboxymphenyl thio group, cometoquin-r-t-octylphenylthio group + l-methanesulfonylphenylthio group, goo-octanesulfonamidophenylthio group, 2-butquinphenylthio group,
Co(2-hexanesulfonylethyl) -! -t
er t-Octylphenylthio group, benzylthio group, 2-cyanoethylthio group, l-ethoxycarbonyltritenylthio group,! - Phenyl J, J, K.

! -tetrazolylthio group, cobenzothiazolylthio group, 2-dodecylthio-5-thiophenylthio group, copheny-3-dodecyl-/, 2. '1-triazolylthio group, etc.).

When R7, RB, R9 or : 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-denlene group, -CH2CH
2-O-CH2C1 (2-1, etc.) Substituted or unsubstituted phenylene group (for example, /.

ψ-phenylene M, /, 3-phenylene group, -Nl(C
O-R7, -CONH- group (R7 represents a substituted or unsubstituted alkylene group or phenylene group).

When the compound represented by the general formula CW) to (■J is present in the vinyl monomer, the linking group represented by R7, R8 or R9 is an alkylene group (a substituted or unsubstituted alkylene group, such as methylene group, ethylene group, /, IO-decylene group, -CH2CH20CH2CH2-1, etc.), phenylene group (substituted or unsubstituted phenylene group, e.g. /, <4-), 22shine group, /, 3-phenylene basis,
-NHCO-1-CONH-1-0-1-OCO- and aralkylene groups (eg, etc.) are included.

In addition, the vinyl group in the vinyl monomer has the general formula (IVJ
〜(■Includes cases where the compound has a substituent other than those represented by J. Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having /~ψ carbon atoms.

Acrylic acid, α
- Chloroacrylic acid, α-alacrylic acid (e.g. methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacryl Ad,
Methyl acrylate, methyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, λ-ethyl quinol acrylate, n-octyl acrylate,
Lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-
hydroquine methacrylate), methylene dibis acrylamide, vinyl esters (for example, vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylate trile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyl toluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (
For example, vinyl ethyl ether), maleic] fA water maleic acid, maleic ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, and λ- and p-
Examples include vinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together.

Compound examples and synthesis methods of the couplers represented by monofunctional formulas from CI [l] to [■] are described in the documents listed below.

The compound of general formula CI) is produced by Shokai Akira! Tar/62j4t♂
etc., the compound of the general formula [■] is 'ff open tO-≠3
For example, the compound of general formula [■] is
7≠//, etc., the compound of the general formula [■] is published in JP-A-Kokai Akiyoter/7/rijO and the same Otsu Q-/7λrigλ, etc., the compound of the general formula [■] is published in the JP-A Showa tO-33! ! λ, etc., and the compound of general formula [■] is described in US Patent 3. O6/, ≠3
Each is listed in 2nd place.

Also, Shikai Shoj♂-μ, 20 Hiroyo, Tokukai Sho! Tar u/4
'fj1. T, same 6? -/772r! 3. Same! Tar 77
7! ! ≠, and the highly color-forming pantyhose groups described in 777, 7, etc., have the above general formulas [■] to [■]
Applies to any of the compounds.

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

(M-/) (M-j) (M-J) (M-μ) (Mr) (λee Otsu) (M-71 [Mr. (M-to) (M-//) (M-/ko) (M-/J) (M-/lI) (M-/j) (M-/'4) (M-/7) n-C6H13 (M-/ri) (M-10) (Mr/) (M--2) (λi, 23) (M-2 Hiromu) し I″i3 (M--r) (M-Kolo) Shi8M17tll (M-, 2J') (M-Jl (M-32) (M-IIo) (M-≠/) Vinegar-←CH2)3 Jiao H3 ■ H3 (M-1I, r) (M-jo) H3 tsu (M-tt) (M-sr) (M-r4) C8H,7(+) M-t7) (M-buco) 6]”113(11 (M-≦yo, x:y=″o:t.

x:y=! 0:! 0 (M- & j) J x 70 mol, preferably / x 10'' mol to r x io -1 mol.

In order to satisfy the characteristics required of a photosensitive material, two or more types of couplers and the like can be used together in the same layer, or the same compound can be used in different combinations. Of course, it may be added to two or more layers.

Couplers can be introduced into silver halide emulsion layers using known methods, such as US Pat. U, 312. The method described in Oλ No. 7 is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl heptatalate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl heptophosphate, tricresyl phosphate, dioctyl butyl 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. dibutyl/ethyl sac/nate, ethyl azelate), trimesic acid esters (e.g. For example, tributyl trimesate).

or an organic solvent having a boiling point of about J00C to tro0C, such as ethyl acetate 1. After dissolving in lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl 7/L=col, methyl in butyl keto/, β-ethoxyethyl acetate, methyl selonorub acetate, etc., it is dispersed in a hydrophilic colloid. . The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

The "reflective support" 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. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with reflective layers or reflective materials, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate. , polyamide film, polycarbonate film, polystyrene film, etc. These supports can be appropriately selected depending on the purpose of use.

The color developer used in the present invention does not substantially contain benzyl alcohol. “Substantially not containing” means i,
oml/ is the benzyl alcohol concentration below and preferably contains no benzyl alcohol.

Further, the color development time is 2 minutes 30 seconds or less, preferably 20 seconds to 2 minutes 30 seconds, more preferably ≠0 seconds to 2 minutes.
It is minute 00 seconds. The color development time herein 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, and includes the so-called transfer time.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an aqueous alkaline solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phenylenediamine/based compounds are preferably used, and representative examples thereof include 3-methyl-≠-amino-N, N
-diethylaniline, j-mefru≠-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-hiro-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl- ≠-Amino N-
Examples include ethyl-N-β-methoxyethylanili/and their sulfates, hydrochlorides, p-toluenesulfonates, and the like.

The color developer conveniently used in the present invention preferably has a pH of ~1λ, more preferably ~//, O, and contains other known developer component compounds. can be set.

ψriege alkaline agent, caustic soda as pH buffer,
caustic potash, carbonate nose, carbonate potash, 3rd grade/sake noda,
Tertiary potassium phosphate, potassium metaborate, borax, etc. are 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 salts are used, such as alkali nitrate, alkali sulfate, etc.

In addition, various chelating agents can be used in the color developer to prevent precipitation of calcium and magnesium. Relie is Bolili/acid acid, aminopolycarboxylic acids,
Phosphonocarvone cl1m, amine polyphosphonic acids,
/-Hydroxyalkylidene-/, /-diphosphonic acid, etc.

Any development accelerator can be added to the color developer if necessary. For example, various pyrimidiram compounds represented by U.S. Patent No. 2.6 Hiro♂, 2C Hiro No., Japanese Patent Publication No. 7603, U.S. Pat. cationic dyes such as, neutral salts such as thallium nitrate and potassium nitrate, Masakiaki≠
≠-2JO4L, US patent! , jJJ, Tata Q, the same.

! 3/, t32, same 1. Rizo, No. 770, same!
, 677, /λ7.

Nonionic compounds such as polythioethers, derivatives thereof, polythioethers, and thioether compounds described in US Pat.

In addition, sulfites such as sodium sulfite, potassium sulfite, potassium bisulfite, and sodium bisulfite, which are commonly used as preservatives, can be added as necessary.

It is preferable to add as little amount as possible if preservation can be maintained.
0-j f/L, more preferably about 0 to 32/L.

Furthermore, hydroxylamines may be added as a preservative. Hydroxylamines include hydroxylamine 7,N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, N,N-di(methoxyethyl)hydroxylamine, etc., and these can be combined with various acids and salts. It may be formed. The amount of these hydroxylamines added is preferably as small as possible if the stability is maintained, and is preferably 0 to 1 O2 per color developer.

In the present invention, an arbitrary antifoggant can be added to the color developer, if necessary. As antifoggants, alkali metal halides such as potassium bromide, sodium chloride, potassium iodide, and organic antifoggants can be conveniently used.

Two or more of these antifoggants may be used in combination, but if fogging can be prevented, it is preferable that the amount added is small.

Examples of organic antifoggants include Pe/Citri 77'-
/L/% t-nitrobenzimitasole, j-nitroinindazole,! -methylbenzotriazole,
! - nitrogen-containing heterocyclic compounds such as nitrobenzotriazole, j-chlorobenzotriazole, 2-thiazolyl-benzimidazole, cortiazolylmethyl-benzimidazole, hydroxyazaindolizine, and/or -
Mercapto-heterocyclic compounds such as phenyl-mercaptotetrazole, -mercaptobenzimidazole, comercaptobenzothiazole, and also mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. 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 photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (Ill
), compounds of polyvalent metals such as cobalt (In), chromium (■), and copper (It), percRs, quinones, nitro compounds, and the like are used. Typical bleaching agents include ferricyanide; dichromate; iron (10) or cobalt (ll
l), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, /, 3-
Complex salts of aminopolycarboxylic acids such as diamino-U-propatoltetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; manganates; nitronophenols, and the like can be used. Among these, the following whitening agents are preferred.

Iron ethylenediaminetetraacetate (Ill) salt Iron diethylenetriaminetetraacetate (ill) salt Iron methyliminodiacetate (Ill)
nl) Salt cyclohexanediamine iron acetate ((II) salt/,!-
Diaminopropane tetraacetic acid iron acetate II) The pH of the base whitening solution and bleach-fixing solution is preferably 3 to 3, preferably pH μ to
? It is. To adjust p 1-1, hydrochloric acid, nitric acid,
Various acids such as sulfuric acid, phosphoric acid, acetic acid, and citric acid, and alkalis such as caustic soda and ammonia may be added as necessary.

If necessary, various accelerators may be used in combination with the bleaching solution and bleach-fixing solution.

After bleach-fixing or fixing, washing with water 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, to prevent precipitation, use water softeners such as inorganic phosphoric acid, amine polycarboxylic acid, and organic phosphoric acid, fungicides and anti-pyre agents to prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum. A hardening agent typified by salt, a surfactant for preventing drying load and unevenness, etc. can be added as necessary. Or West, Photographic Science and Engineering (L, E, West, Photo.

Sci, Eng, ), Volume 3, 3ILttI~3!
Compounds described in Tapage f/ritz) etc. may be added.

The addition of chelating agents and anti-piping agents is particularly effective.

Furthermore, in order to improve the stability of the washing water, it is also an effective means to use ion-exchanged water in which the calcium and magnesium ions are reduced to below 1 ppm.・In the washing process, it is common to use countercurrent washing in tanks larger than one to conserve water. Furthermore, instead of the water washing process,
-r! A multistage countercurrent stabilization treatment step as described in Kou No. 3 may also be carried out. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various peak levels (e.g., borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia) to completely adjust the membrane pH (e.g., pH J ~ , monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin are representative examples. In addition, water softeners (inorganic phosphoric acid,
(aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosbocarboxylic acid, etc.), fungicides (benzointhiazolinone, irithiazolone, goutiazoline benzimidazole, halogenated phenols, etc. 1, world M5 agent, firefly) Various additives such as optical brighteners and hardeners may be used, and two or more compounds having the same or different purposes may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium 61, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a liJ pH adjusting agent after the treatment.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. For this purpose, it is preferable to use various precursors of color developing agents.

The silver halide color light-sensitive material of the present invention may contain various /-phenyl-
It is also possible to incorporate 3-pyrazolidones. A typical compound i'i is from JP-A-Shoj. ! 3≠ issue, WatarujjJ'-jtO
! Jr. and the same! -//! It is described in ≠3r issue etc.

Various treatment liquids in the present invention are used at 10'C-to'c. The standard temperature is between 0 and 3R, but higher temperatures may be used to accelerate processing and shorten processing time, or lower temperatures may be used to improve image quality and stability of the processing solution. Can be done. In addition, due to the economical cost of photosensitive materials, it was possible to save money in West Germany (i)! Treatment with cobalt or hydrogen oxide intensification as described in U.J. 2A, 770 or U.S. Pat.

A heater, a degree sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each washing bath as necessary.

The silver halide emulsion used in the emulsion layer of the silver halide photographic light-sensitive material of the present invention may be any known silver halide emulsion.

The tin halides preferably used in the present invention are silver bromide, silver chlorobromide and silver chloride which do not substantially contain silver iodide, and preferred examples include silver chloride bromide containing 2 to 77 moles of silver chloride. It is. In order to obtain an emulsion with sufficient sensitivity without increasing fog, it is preferable that the silver bromide content is 20 moles or more; 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 development of bromide ions when a light-sensitive material containing silver bromide is run in a processing solution.
The accumulation in the liquid is reduced, and the developer itself becomes highly active, which is very favorable for rapid processing. The silver halide grains may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed. For example, for silver chlorobromide grains having different phases, the average halogen composition may be a grain with a silver sibromide-rich core or single or multiple layers within the grain. Further, the particles may have a core rich in silver chloride than the average Rodan composition, or may have a single or multiple layers within the particles.・
・The average grain size of silver rhodanide grains (in the case of spherical or near-spherical grains, the grain diameter is the grain size; in the case of cubic grains, the principal is the grain size and the projected area is the average) is λμ or less is preferably 0.1μ or more,
Particularly preferred is /μ or less O1/! μ or more.

The particle size distribution may be narrow or wide. Average particle size ±p in particle number or weight.

A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 90% or more, particularly 93% or more of all grains are contained within the grain size can be used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodispersed silver genide emulsions with different grain sizes are mixed in the same layer or emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion 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.).
r), may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Tabular grains may also be used, especially when the length/thickness ratio is t or more. An emulsion may be used in which the above tabular grains account for 50% or more of the total projected surface species of the grains. 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 latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is P, Glafkide.
Written by Chimie et Physique Pho
tographique (Paul Monte 1, 1967), O, F.

Photographic Emuls by Duffin
ionChemistry (Focal Pres.
s, / 9 t A year], V, L, Zelikma
Makingand Coatin by n et al.
g Photographic Emulsion
(Focal Press, 1997.U.), etc. In other words, any of the acid method, neutral method, ammonia method, etc. may be used, and soluble silver salt and soluble halogen salt may be used. As a method for reacting the salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). A conversion method in which a halide salt is added to form a less soluble silver halide can also be used.As a form of simultaneous mixing method, the pAg in the liquid phase in which silver halide is formed is kept constant. It is also possible to use the so-called Chondrold double-jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium 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 ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (e.g. ammonia, Rodankali or US Pat. No. 3.27/137, JP-A-Shoj
/-/2JtO issue, JP-A-53-ZA2≠Or, JP-A-J3-/≠u3/ri, JP-A-341-1007/7 or JP-A-5≠-/j! The thioethers and thione compounds described in ♂Co.R, etc.) can be used in precipitation, physical ripening, and chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, Nudel water washing, 70-curation sedimentation method, ultrafiltration method, etc. 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 method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds): Metal Compounds (e.g., complex salts, Pt, I r, Pd, Rh% F
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as e) can be used alone or in combination.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye. The pigments used include cyania color 1
/,,/'Russianine color L includes cyanino dyes, complex melonanine dyes, holopolar cyanine dyes, heminanine dyes, styryl dyes, and hemioxonol dyes.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (
For example, U.S. Patent No. 2, 33, 30, 3. Otsu!
1,72/), aromatic organic acid formaldehyde condensates (e.g. U.S. Pat. No. J, 7173.!1)
0), cadmium salts, azaindene compounds, etc.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance.

A variety of color couplers can be used in the present invention. Useful color couplers are cyan, magenta and yellow colored couplers, typical examples of which include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds and open-chain or
There are heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that may be used in the present invention are provided by Research Disclosure (RD)/7t'
IJc/y7r year/month) ■-D term and y/17/7
It is described in the patent cited in (/7///).

The color coupler incorporated in the light-sensitive material is preferably diffusion resistant by having a last group or by being polymerized. The amount of silver coated is smaller in the two-color coupler substituted with a leaving group than in the four-color coupler in which the coupling active position is a hydrogen atom. Also useful are couplers in which the coloring dye has adequate diffusivity, colorless couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected aziladamide coupler. A specific example is U.S. Pat.
No. 407.210, No. 2,173.067 and No. 3. It is described in Ko A j , No. 106, etc. The use of two-equivalent yellow couplers is preferred for the present invention;
U.S. Patent No. 3. ≠01, / Rihiro No. 31 Hiro≠7.9
λ No. 3. 33, 60/No. and Hiroshi Q2
Ko.

Oxygen atom separation type yellow couplers described in No. t20, etc., or Tokuko Shoyo J'-/“073, U.S. Patent No. ≠, Hiro 0°/, 7yo 2, U.S. Patent No. μ
No., RD/10!3 (/7 years μ month), British Patent No. 1
．． II2, No. 020, West German Published Application No. 1, Co/9. ri No. 77, same No. ko, Ko Otsu/, Jt No. 1, same No. 2, 32,
! Typical examples thereof include the nitrogen source separation type yellow couplers described in No. R7 and No. 2゜≠33,112. α-piparoylacetanilide couplers have excellent color fastness, especially light fastness.
On the other hand, α-benzoylacetanilide-based cazolers provide high color density.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based power pullers, which are disclosed in US Pat.

Naphthol couplers described in US Pat. No. 223, preferably US Pat.

Typical examples include the oxygen atom-eliminating type two-equivalent naphthol couplers described in Japanese Patent No. 6,39, No. 1,22 No. 1-33, and No. 200 of Japanese Patent No. 6,39. A specific example of a phenolic coupler is U.S. Pat. No. 1, 36? , Ri 2 De No. 2.101.171, Ri No. 2,772,162, Ri No. 2. It is described in Zari r, rxtz issues, etc. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is an alkyl group higher than ethyl group in the meta position of the phenolic nucleus described in US Pat. Phenolic cyan coupler having U.S. Pat. No. 2,772,162, U.S. Pat.
Same No. 41. /26. JFt No., μ, 33≠, 0//
No., μ, 3 cores.

No. 773, West German Patent Publication No. 3,322,7 Kota, and Japanese Patent Application No. 12J-
Dianlyamino-substituted phenolic couplers and U.S. Pat.
, 7j7, etc., has a phenylureido group at the 2-position and! These include phenolic couplers having an anruamino group at the - position.

A coupler in which the coloring dye has appropriate diffusivity can be used in combination. Such couplers are described in U.S. Pat. No. 44.
J4j, 237 and British Patent No. 2,/21,170
A specific example of a magenta coupler is given in European Patent No. 24.
．． Specific examples of yellow, magenta or cyan couplers are described in No. 170 and German Patent Application No. 3,23μ, j33.

The dye-forming couplers and the above-mentioned special couplers may form a dimer or higher polymer, except for couplers in which the color-forming dye has diffusivity. PoIJ-? Typical examples of dye-forming couplers are described in U.S. Pat. Specific examples of polymerized fuzenta couplers are described in British Patent No. 2.
ioco, No. 173 and U.S. Patent No. ≠, El, 7,21
It is stated in No. 2.

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 various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. This can be cited as an example. In the oil-in-water dispersion method, a high-boiling organic solvent with a boiling point of /yz"c or higher and a so-called auxiliary solvent with a low boiling point are dissolved either alone or in a mixture of the two, and then water is dissolved in the presence of a surfactant. Or finely dispersed in an aqueous medium such as an aqueous gelatin solution. Examples of high boiling point organic solvents are U.S. Pat.
λ, No. 027, etc.

Typical amounts of color couplers used are in the range o, ooi to 1 mole per mole of silver rhodide, preferably yellow couplers &-+n ha/-p.
Pl ha l/l gukiru, 0.0 for magenta coupler
03 to 0.3 mol, and /uncoupler o, o
ox to 0.3 mole.

The light-sensitive materials produced using the present invention may contain hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenols as color antifogging agents or color mixing inhibitors. It may also contain derivatives and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic antifading agents include no-idokuquinones, Δ-hydro, xychroman a, j-hydroxycoumarans, spirochroman'1JA, p-alcoquinephenols, hindered phenols mainly including bisphenols, and gallic acid derivatives. Typical examples include methylenedioxybenzenes, amine phenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Also (bissalicylaldoximad)
Metal complexes such as nickel complexes and (bis-N,N-dialkyldithiocarbamado)nickel complexes can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
U.S. Patent No. ≠, 24. A compound having a hindered amine and a hindered phenol fractional structure in the same molecule, as described in No. 3, gives good results. In addition, in order to prevent deterioration of maze/red dye images, especially deterioration due to light, JP-A-Sho rt-ir! The spiroindanes described in Ptt, t≠, and the hydroquinone diether or monoether substituted chroman systems described in JP-A Shoyo r-rqr3r give preferable results.

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 preventing matahyradiation or halation.

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 be used in the form of dispersions.

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.

Gelatin includes general-purpose lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, etc.

Phot, Japan, A/&, 70 pages (/ri≦t
Enzyme-treated gelatin as described in ) may be used, and gelatin hydrolysates and oxygen-decomposed products may also be used.

In the photographic material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer.

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 Research Disclosure/71,
143 (/ri7g/, February) and /rylt (
/P75F/January).

The invention 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 two or more emulsion layers having different sensitivities, and an insensitive layer may be present between λ or more emulsion layers having the same sensitivity.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

(Example) The present invention will be further explained below with reference to Examples. On one of the prepared paper supports, a number of color photographic papers 1 to 1 were prepared with different magenta couplers and water layer compositions as shown in Table A.The coating solution was prepared as follows.

Preparation of first layer coating solution Yellow coupler (al/q, /y and color image stabilizer (b)
)) Hiroshi, uf to 27.2 ml of ethyl acetate and solvent (C)
Add a 7° tab to dissolve, and add this solution 'f (containing 10% sodium dodecylbenzenesulfonate) to 1/0
4 gelatin aqueous solution/rrtrtl. On the other hand, silver chlorobromide emulsion l silver bromide rOmoL, heg7θ5'/
(containing Kq) and the blue-sensitive sensitizing dye shown below at a concentration of silver chlorobromide/m
A blue-sensitive emulsion with a matte strength of 7.0 x 10' per o1 was prepared by wyoyfA. Mix and dissolve the emulsion dispersion and emulsion, adjust the gelatin tone so that it has the composition shown in Table A,
A seventh layer coating solution was prepared. .

The coating solution for the 2nd round to No. 7 was also prepared in the same manner as the first layer coating solution. As a gelatin hardening agent for each layer, /-oxy-3,3-dichloro-5-) riazine sodium salt was used.

The following spectral enhancers were used for each emulsion.

Night-sensitive emulsion/d (Silver halide/mot Schiff, Ox/0' moL addition) Green-sensitive emulsion layer 5O3HNCC2H5) 3 C halide complex/mot <A, 0X10' mat addition) 5O3HNI C2H3)3 (Halogenated 7.0×10 mol added per silver/mot) Red-sensitive emulsion layer (silver halide/added 0×10 mol per mot) 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 SO3K 303 K coupler, are as follows.

ral yellow coupler rbl color image stabilizer ShiH3 (cl solvent (f) Color image stabilizer Rigo 3CH3 tg) Solvent fhl UV absorber C4] ” /:yo:3 mixture C molar ratio) (i) Color mixing prevention agent (jl solvent (grsec) (iso CgH1gO+yP=O H9ζsecl The magenta couplers used are as follows.

The amount of silver coated on sample ■C No. 3 J- is 0.3! ? /m2 and 7.

(?J Sample @ Sample 0 Exemplified compound M-≠2 Sample @ Exemplified compound M-1j Sample Exemplified compound M-Hiroshi! Next, each sample from ■ to
Using a FWH type light source with a color temperature of 3λoo 0K), stepwise exposure for sensitometry was provided through blue, green, and red filters. The exposure at this time was 2 with an exposure time of 0.3 seconds.
The exposure amount was adjusted to be that of ♂QCMS.

The above-mentioned exposed photosensitive material was processed in the following processing steps.

[Processing process) C temperature) C time) Color development process 3r0c λr OO // Bleach-fixing process 3♂QC // o o // Water washing process 2μ ~ 33
°Ci'oo" Drying process 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.

C color developer prescription) Five vinegar 2. Of 2.09 Benzyl alcohol /j-- Diethylene glycol 10m1 -Na2SO3
2,0? 2.09 KBr O, At O, l,?
Hydroxylamine sulfate 3.0? 3.0? l-amino-3-methyl-N-ethyl-N-[β-[methanesulfonamido)ethyl]-aniline sulfate g, jr? Hiro! ? Add water 10oornl 10oornl
pHio, rr 10. rr Further, formulations in which various compounds of general formula (1) shown in Table 7 were added to formulations A and B were designated as C-J.

Next, the recipe for the bleach-fix solution is shown.

C bleach-fix solution formulation) Ammonium thiosulfate (!≠wt 1 110ml1Na2
SO3/j? NH4CFe fII[l f EDTA 1]j
! S'EDTA-2Na
4′? Total volume including water: 1000ml
Table 1 shows the results of processing the samples from ■ to ■ using the plastic formulations of A to J, and measuring the minimum and maximum concentrations of the resulting magenta dye using a Macbeth densitometer. Indicated.

When the compound of the present invention is added to VC in the presence of benzyl alcohol, a significant magenta fog is produced in the results. However, when added to a color developer without benzyl alcohol, (
A7 to IO), no fog was generated and sufficient color development was observed. Historically, it can be seen that when a magenta coupler represented by the general formula fI[+ is used, even better coloring properties are exhibited. Also, almost the same results as above were obtained when the color development step time was shortened by 7 minutes.

[Example-]

In Examples/, the amount of each compound of the present invention added,
Even if it is set as oyit and processed in the same manner as in Example/, the same effect as in Example/ is obtained.

[Example 3] A multilayer color photographic paper was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

11 Coating liquid preparation Yellow coupler (a) /2, /2 and color image stabilizer 1b
) Hiro, ≠ ethyl acetate core, -1 and solvent (c17.
This solution was emulsified and dispersed in a 10% aqueous gelatin solution containing 10 rml of sodium dodecylbenzenesulfonate.

On the other hand, silver bromide emulsion f silver bromide/, Omot4, Ag70f
/Kg) and silver chlorbromide/
A blue-sensitive emulsion was prepared by adding 6.0 x 10' mot per mot. A first layer coating solution was prepared by mixing and dissolving the emulsified dispersion and adjusting the gelatin concentration to have the composition shown in Table B.

The coating liquids for the second layer to the seventh layer were also prepared in the same manner as the first layer coating liquid. l-oxy-3,j'-dichloro-s-triazine sodium salt was used as the gelatin hardening agent for each layer.

The following book was used as the spectral sensitizer for each emulsion.

Blue-sensitive emulsion layer 10 silver genide/r per mot, 0x10'mo
t addition) SO2NH (C2H513 (HaCI silver genenide/mot equivalent?) u, O x 10 'm
ot addition) SO2NH (C2H513C 7.oxto-5mot addition per silver halide/mot) Red-sensitive emulsion layer C2Hs Iec2) 15 (Ol per silver halide/mot X/<7 mo
Addition of A) 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.

(al yellow coupler (b) color image stabilizer (c) solvent (dl color mixing inhibitor (e) solvent (f) color image stabilizer 1gl solvent (hl molar ratio of /:!:3 mixture C of ultraviolet absorber) Koni/a Compound (Weight Ratio) The color photographic paper obtained as described above was subjected to wedge-shaped exposure, and then processed in the following processing steps.

Processing process Temperature Time Color development (jj'cl Bleach fixing listed in Table λ fJjocl Ilj second rinse / (3
Evening 0C) Rinse for 20 seconds λ (310C)
20 seconds') 7th j LJjoC) 20
Dry for seconds (♂o 0cl Ao seconds used 1.The resulting can liquid is as follows.

Triethanolamine 1oyN, N
-Diethylhydroxylamine Sodium sulfite 0.22 Potassium carbonate
30? EDTA-uNa-coH20
λ is potassium bromide 0.07? ≠-Amino-3-methyl-N-ethyl-N-Cβ-(methanesulfonamido)ethyl]-Aniline, sulfate! , 09 Fluorescent brightener f Hiro, Hiro'-diaminostilbene series, Ciba Geigy) UVITEX CK) J, add water to 10 ooml pH 10,
λO Bleach-fix solution EDTA Fe ((II) NH4・-2H2
0t ojEDTA*, 2Na-2H20@S' Ammonium thiosulfate (70%) 120ml 7
Sodium acid /A? add water
1000trLlpH, rinse solution) /-Hydroxyethylidene/, 7'-diphosphonic acid + 10 liters 1/, Am bismuth chloride 0.31? Polyvinylpyrrolidone 0.2jf? Ammonia water (264)
2.1mlml Sodium Nitriloacetate
/, o9EDTA @HiroshiHO, rf? Sodium sulfite /, 01j-chlorocomethyl-μm isothiazolin-3-one! O ■ Formalin LJ74) 0. /m/add water
1ooo-pH7.0 Table 2 shows the results of measuring the obtained sample using a Dmin and Dmaxk Macbeth densitometer.

Based on the present invention (41!~/7), the fog was low and sufficient color development was obtained, whereas the presence of benzyl alcohol increased the fog (&/-1/r1/r,
-0%-/), color development is reduced in the absence of the accelerator of the present invention. (Mu22), [Example≠] Instead of I-to (glycine) in Example 3, Table 2,
Similar to Example 3, excellent photographic properties were shown when the compound of the present invention was included, even when experiments were conducted using the compounds 1-μ, choline, DL-serine, and hydroxyethylmorpholine individually.

C) Effect of the invention) In addition to the compound represented by the general formula rI), the aforementioned compounds such as tetramethylammonium acetate, choline, choline chloride, and hydantoic acid caused significant fogging when used in a normal color developer. However, when benzyl alcohol was not present and the development time was short as in the present invention, excellent color development and development accelerating effects were exhibited.

This was particularly noticeable in light-sensitive materials containing a magenta coupler represented by the general formula rIIl.

Further, since the compound of the present invention does not have low water solubility like benzyl alcohol, the present invention is preferable since the need for an auxiliary solvent such as diethylene glycol is unnecessary or greatly reduced.

Further, among the compounds of the present invention, compounds represented by the general formula CI) are preferred because they improve the stability of the developer.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment 1962, 2 @ 1st, Patent Office Chief Palace 1, Indication of the case: 1986 Patent Application No. 373, Tata No. 2, Name of the invention: Silver halide color photographic sensitization Material processing method 3, relationship with the case of the person making the amendments: Telephone number for applicants for expenses (406)
2537 4. Subject of amendment: “Claims” column of Statement a,
The statement in column 5 of the "Detailed Description of the Invention" and the "Claims" section of the description of the contents of the amendment is amended as shown in the attachment.

The statement in the "Detailed Description of the Invention" section of the specification is amended as follows.

fil　Correct page 7 as shown in Attachment-2.

(2) Correct the 2nd to IO pages as shown in Attachment-3.

Attachment 2, Claims (1) A silver halide color photographic material having at least -1 silver halide emulsion N on a reflective support, substantially free of benzyl alcohol, and A compound represented by the following general formula (1), tetramethylammonium acetate), SF! 2 minutes in a liquid solution containing at least one of the following: chloride, choline chloride, hydantoic acid, allylamine, aminoguanidine sulfate, 0-aminobenzoic acid, 0-7 minobenzyl alcohol. Silver halide power 2-A method for processing a photographic light-sensitive material, characterized in that the processing is performed in a time of 30 seconds or less.

General formula (R1 is an alkyl group having 1 to 70 carbon atoms, R2 and R3 are each a hydrogen atom, or 7 to 7
an alkyl group having 0 carbon atoms, R1-R3
represents an alkyl group, (2) the silver halide color photographic light-sensitive material contains a magenta coupler of the following general formula (II); A method for processing silver halide color photographic materials.

General formula (I[) (wherein Rb represents a hydrogen atom or a substituent, yt represents a group that can be separated by a coupling reaction with an aromatic primary amine oxidized crude drug, and Za.

zb or Zc is a methine group, substituted meth/group, =N- or -
It represents NH-, and one of the Za-Zb bond and Za-Zc bond is a double bond, and the other is a single bond. ) Attachment - (1) A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support
Compounds that do not substantially contain alcohol and are represented by the following general formula (1), tetramethylammonium acetate, choline, choline chloride, hydantoic acid, allylamine, aminoguanidine sulfate, O-
A silver halide color photographic light-sensitive material which is treated with a color developer containing at least -m selected from aminobenzoic acid and 0-aminobenzyl alcohol for a time of 2 minutes and 30 seconds or less. How to do it.

(2) The silver halide color photographic light-sensitive material contains a magenta coupler represented by the following general formula (If).
ni'? The method for processing a silver halide color photographic light-sensitive material according to (1) above, in which the silver halide color photographic light-sensitive material is made to have a trepidation characteristic.

It was found that this can be effectively achieved.

Attachment 3 General formula (1) R1 is an alkyl group having /-10 carbon atoms, preferably an alkyl group having from fi to j carbon atoms. R
2 and R3 are each a hydrogen atom or an alkyl group having io carbon atoms, preferably a hydrogen atom or an alkyl group having 7 to 1 carbon atoms.

When R1-R3 in general formula (1) represents an alkyl group, specific examples include methyl group, ethyl group, 1-propyl group, n-hexyl1k-17chlorohexyl group, decyl group,
etc.

These alkyl groups may be substituted with a chlorine atom, a carboxyl group, an alkoxy group, etc.; When R1, R2, and R3 represent an alkyl group, R1 and R
2. R1 and R3, R2 and R31, or R1, R2 and R3 may be linked to each other to form a ring.

Note that this nitrogen-containing heterocycle further contains a heteroatom (fl'
ll, oxygen atoms, sulfur atoms, etc.).

The compound represented by general formula (1) is an inorganic acid (for example,
It may be in the form of a salt of hydrochloric acid, sulfuric acid, etc.) or an organic acid (eg, oxalic acid, acetic acid, p-toluenesulfonic acid, etc.).

Specific 9'lJ of the compounds used in the present invention are shown below, but the invention is not limited thereto.

I-/trimethylamine! -2 Diethylamine 1-j Methylamine I-≠ Triethylamine 1-s Diethylamine 1-+ Diisopropylamine 1-7 Ethylamine 1-4 Dimethylamine I-ta 6-aminohexanoic acid 1-10 Glycine 1-// /, /- Aminoundeconic acid 1-/λ L-
(g)-7 Stain Hydrochloride l-73 Benzylamine 1-/g D,L-serine 1-/j Morpholine 1-/lo-aminobenzyl alcohol 1-/7 Quinuclidine 1-it Hydroxylethylmorpholine 1-/ 9
Tetramethylammonium acetate l-CoOcholine ■-27 Choline chloride ■-2λ Hydantoic acid 1-. 2j Allylamine I-2≠ Aminoguanidine sulfate I-2! 0
-Amine benzoic acid The compounds described above and in claim 11) may form salts with various organic and inorganic acids.

The amount of these compounds added to the color developer is preferably 0.0/? per lt of the color developer. ~20t1, preferably 0. /? ~10? It is.

Claims (2)

[Claims] (1) A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support, substantially free of benzyl alcohol, and having the following general formula (
Compounds represented by I), tetramethylammonium acetate, choline, choline chloride, hydantoic acid, allylamine, aminoguanidine sulfate, o-
Aminobenzoic acid, L-(+)-cysteine hydrochloride, benzylamine, DL-serine, morpholine, o-
Processing of a silver halide color photographic light-sensitive material characterized by processing in a color developer containing at least one selected from aminobenzyl alcohol, quinuclidine, and hydroxylethylmorpholine for a time of 2 minutes and 30 seconds or less. Method. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^1 is an alkyl group having 1 to 10 carbon atoms, and R^2 and R^3 are each a hydrogen atom or 1 to 10 an alkyl group having 5 carbon atoms.) (2) The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material contains a magenta coupler represented by the following general formula (II). processing method. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Rb represents a hydrogen atom or a substituent, and Y_1 is a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developing agent. , 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. )