JPS62275259A - 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 developing time of 2min. 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 <=4X10<-3>mol/l bromine ions within a developing time of 2min. Said photosensitive material has at least one silver chlorobromide emulsion layer containing substantially no silver iodide but >=50mol% silver chloride, and 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, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The invention relates to a method for processing silver halide color photographic materials, especially benzyl alcohol! The present invention relates to a processing method in which the color development time is significantly shortened.

(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 the color developer to speed up color development is currently being used in the processing of color photographic materials, especially color paper, due to its strong color development promotion effect. Widely used.

However, when benzyl alcohol is used, diethylene glycol, triethylene glycol, alkaliamine, etc. are required as g and Ill because of its low water solubility. However, these compounds have the same pollution burden as benzyl alcohol.
30D and C0I), it is preferable to remove benzyl alcohol for the purpose of reducing the pollution load.

Even if you use this bath additive, the amount of Verzyl Alcohol 75
r: Since it takes time to understand, it is better not to use verzyl 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 flow rate of the developer component is delayed, the image storage stability of the processed photosensitive lumber 1 may be adversely affected.

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

Conventionally, color development has generally been processed in 3 to 1 minute minutes, but with the recent shortening of finishing delivery times and the reduction of one-step work, there is a desire to shorten the processing time. Ta.

However, removing benzyl alcohol, which is a color accelerator, and developing time! If the length is shortened, construction work that will result in a significant decrease in color density is inevitable.

During this time, in order to solve Vw, various color development enhancers (for example, U.S. Pat. No. 2,960,970, Kota/j/K
No. 7, same number, 9≦, No. 903, same λ.

30u, No. 921, 9.03♂, Q2! No., same number, /
/9. tt2, British Patent/, 'ljj, 11t73, JP-A-4,2≠! θ, same! ! -62 Hiroj No. 1, same j! -A21-, same jj
-4j Hiromu! No. 3 - No. rr-jOj3, No. tO-/4
Here, No. 6, Tokuko Sho/-/Oichi No. 2-Dojj-Hiroshi 27
Even when the compound described in No. 2) was used in combination, sufficient color density could not be obtained.

In addition, a method of incorporating a color developing herbal medicine (for example, US Patent No. 3)
719μ Octopus, IWlJ J 4L! ! No. Y.

331 is No. 97, and JP-A No. 64-/; 235.

Same rA-/A13J issue, same! 7-ta 7! No. 31, same j7
Even if the method described in No. 43jtj, etc. is used, it is not an appropriate method because it has drawbacks such as slow color development and fogging.

Also, a method using a silver chloride emulsion (for example, JP-A-Shoj-
9j3≠j issue, same! Tar 2323 Hiro 2.

Although the method described in No. 40-/Li/Hiro-θ is an excellent method for shortening color development, fogging tends to occur in the presence of benzyl alcohol, and it is not a suitable method for practical use. None.

As described above, no method has been found for obtaining a sufficient color image in a short time of less than 11 minutes using a color developing solution that does not substantially contain benzyl alcohol.

(Problems to be Solved by the Invention) Color developers for silver halide color photographic materials include:
Bromine ion is generally used as an antifoggant, and its addition is very effective! XI0 3~nooxyo
n]o-e/no. By the way, bromine ion I
! Although it is easy to think that color development can be improved by reducing the amount by 1 degree, in the case of processing that contains benzyl alcohol and takes more than 3 minutes, as in the processing of conventional color photographic paper, .

If the amount of bromide ions was reduced below the above concentration, a problem occurred in that a significant increase in fog occurred, and it was not possible to reduce the amount of bromide ions.

Also, as a method to shorten color development time.

A method using an emulsion consisting essentially of silver chloride is disclosed in JP-A-40-/9/%tO, Ibid. ? -37≦31, and the same number? Although it is described in JP-A-10♂ E-33, etc., fogging occurs when processed with a color developer containing benzyl alcohol, and JP-A-KOKAI Shouli T-9TA3SU5 and J9-KO323U2 Anti-fog technology described in the issue! Even when used, it was insufficient.

Therefore, an object of the present invention is to provide a silver halide color that does not contain benzyl alcohol in a color developing solution and that produces sufficient color development with little fog even in a short color development time of 2 minutes or less. The purpose of this invention is to provide a method for processing photographic materials.

(Means for solving problems) The object of the invention was achieved by the method described below.

That is, (1) a color photographic light-sensitive material containing at least -JΦ100 silver halide emulsion F- on a reflective support! , substantially free of benzyl alcohol, and Ixlo m
Bromine ion below o-e/-e! 1. A method for processing a silver halide color photographic light-sensitive material, which is characterized in that color development is carried out in a color developer containing a color developer for 2 minutes or less.

(2) The silver halide color photographic light-sensitive material has a silver chlorobromide silver halide emulsion layer containing substantially no silver iodine and at least 50 mol % of silver chloride. 8. The method for processing a silver halide color photographic light-sensitive material according to item 7, wherein the material is a photosensitive silver halide color photographic material.

(3) Processing of the silver halide color photographic material according to item 7, characterized in that the silver halide color photographic light-sensitive material contains a magenta coupler of the following general formula (1). Method.

General formula (1) (wherein R, b are hydrogen atoms or substituted M, ?: represents, Y
l represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developing agent.

Za, zb or Zc is a methine group, substituted methine group, =N-
or -NH-, and a Za-Zb bond and Z b -Z
One of the c bonds is a double bond and the other is a single bond. ) In the present invention (2), the method of significantly reducing the bromide ion concentration in the color developer and improving the color development was unrealistic due to the occurrence of a lot of fog in conventional processing methods.However, The fact that by removing benzyl alcohol and using a color development time of 7a-2 minutes or less as in the present invention, there is no fogging and furthermore, the color development is significantly improved is completely unexpected. there were.

Also, paper containing silver chloride! By using a silver chlorobromide emulsion with a concentration of θ mol % or more, the occurrence of fog is reduced, and the chest color is improved, and furthermore, by using a magenta coupler represented by the general formula Color development was obtained.

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

In the general formula [I], R and b represent a hydrogen atom or a substituent, and ¥1 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 Zc are methine, substituted methine, =
Represents N- or -NH-, and combines Za-Zb bond and zb-
Among the Zc bonds, -10,000 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, Rb or)′
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 multimer of two or more members.

In the general formula [1], a multimer is one in which two or more of the general formulas (11) are included in the 7 molecules, and one screw or a polymer coupler is also included in this. Here, the polymer coupler may be a homopolymer consisting only of a Ii-mer (preferably one with a vinyl group, hereinafter referred to as a vinyl monomer) having a moiety represented by the general formula [l], or an aromatic Copolymers may be made with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of the -grade amine developer.

What is the compound represented by the general formula [l]? It is a membered-ring-5-membered ring fused nitrogen heterocyclic coupler, and its color-forming mother exhibits isoelectronic aromaticity with naphthalene.

Aza usually has a chemical structure recognized as ntalene. A preferred coupler among the couplers represented by the general formula [■]
The H-compounds include lH-imidazoC'+'-b]pyrazoles, lH-pyrazoloC'+5-b]pyrazoles, 11
-1-pyrazolo[r,/-c]C','+''
) Triazole, /'H-pyrazolo C1, j-b
[c/, 2.9] triazoles, lH-pyrazolo[l
,rd]tetrazole and/H-pyrazolo[/,
s-a] benzimidazoles, and have the general formula [■) CII+] [:IV] [■] [■] and [■
Among these compounds, particularly preferred are [IV] and [■].

[1) I:m] [IV] [V] General formula [■]
~CVl+ ], the substituents R,,, R, 2 and R3 are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an arylthio group,
Heterocyclic okyne group, acyluoquine group, carbamoylamino group, silyluoquine group, sulfonyluoquine group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic group thio group, alkoxycarbonylamino group, aryloquine carbonylamino group,
It represents a sulfonamide group, a carbamoyl group, an anhydrous group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloquine carbonyl group, and YI is a hydrogen atom, a halogen atom, a carboxy group, or an oxygen atom, a nitrogen atom, or a sulfur atom. The group that binds to the carbon at the coupling position through the coupling-off group is represented by D.

a,, It2, R, 3 or Y is a covalent group,
Screw body? This also includes cases where the formation descends. Also, general formula [■]
When the moiety represented by ~[■1] is present in the vinyl monomer, R7, R2, or R3 represents a simple bond or linking group, and through this, the moiety represented by the general formula [■] ~ [■] The vinyl group is bonded to the vinyl group.

Furthermore, f1 is R, , R2 and R3 are hydrogen atoms,
Halogen atoms (e.g. chlorine atom, odor atom, etc.), alkyl groups (e.g. methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, J-(2,
it-di-t-amylphenoxy)propyl group, codedecyloxyethyl group, 3-phenoquinepropyl group, 2
-hequinolsulfonyl-ethyl group, cyclo is methyl group,
benzyl group, etc.), aryl group (e.g. phenyl group,
Ter[--y” Terphenyl M”, J, K 7
t 7 mylphenyl group, l-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group, Nietzschenyl group, two-pyrimidinyl group, two-penzothiazolyl group, '4), , alkoxy groups (e.g., methquine, ethquine, two-methoxyethquine, codedecyloxyethquine, λ-methanesulfonylethoquine group, etc.), aryloxy groups (e.g., phenoxy group, dimethylphenoquine group, etc.) , a t-butylphenoxy group, etc., a heterocyclic okyne group (e.g., a two-benzimidazolyluoquine group, etc.), an acetoxy group (e.g., an acetoxy group, a hexadecanoyl okine group, etc.),
Carbamoyl oxene group (e.g., N-phenylcarbamoyloxy group, heethylcarbamoyl oxine group, etc.)
, nilyruoxy groups (e.g., trimethylnryluoquine groups, etc.), sulfonyluoquine groups (sidelight, dodecylsulfonyluoquine groups, etc.), acylamino groups (e.g., acetamido groups, benzamide groups, tetradecaneamide groups, α
-(,2゜Goozi-t-amylphenoquine)butyramide group, γ-(J-t-phthyl-9-hydroquinphenoxy)butyramide group, α-1g-(g-hydroxyphenylsulfonyl)phenoxy)decaneamide^(, etc.), anilino groups (e.g., phenylamino group, cochloroanilino group, 2-chloro-S-tetradecanamideanilino group, cochloro-S-tetradecanamidoanilino group, cochloroanilino group, N-acetylanilino group, two-chloroanilino group, two-chloroanilino group, two-chloroanilino group, -(3-[-phtiluda-hydroquinphenoxy)dodecanamido)anilino group, etc.), ureido group (
For example, phenylureido group, methylureido group, N,
N dibutylureido group, etc.), imide group (e.g. N
- srunamido group, 3-penzylhydantoynyl group, cu(-monoethylhexanoylamino)phthalimide group,
), sulfamoylamino group (for example, N,N-dibropyrus/l/7 amoylamino group, hemethyl-N-
decylsulfamoylamino group, etc.), alkylthio group (e.g., methylthio group, octylthio group, tetrazonorthio group, twophenokyreethylthio group, 3-phenoquinepropylthio group, J-(S<-1- butylphenoquine) propylthio group, etc.), arylthio group (e.g., phenylthio group, -1-butoquine-s-t-ofnalphenylthio group, 3- is ivy decylphenylthio group, tricarpoquinophenylthio group, cootetradecanamide) phenylthio group, etc.), heterocyclic thio group (e.g., 2-pensinanarlylthio group, W), alkoginocarbonyl 7'mino group (e.g., methoxysulfonylamino group, tetradenyloxylponylamino group, etc.) ), azoleoxysulfonylamino groups (e.g., 2-enoxycarbonylamino group, 2-butylphenoxycarbonylamino group, etc.), sulfonamide groups (e.g., methanesulfonamide group, hexadecanesulfonamide group, benzenesulfone amide group, p-)luenesulfonamito group, octadecanesulfonamide group, dimethylone-r-t-butylbenzenesulfonamide group, etc.), carbamoyl group (for example, N-ethylcarbamoyl group, N,N-dibutyl carbamoyl group, N-
(2-todenluoquinethyl)carbamoyl 2V, N-
Methyl-N-dodecylcarbamoyl group, N-1j-(-
, goosey tert-amylphenoquine)propyl)carbamoyl group, etc.).

Acyl group (e.g., acetyl group, (co, l-ter
! -amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl group (e.g. ~-ethylsulfamoyl l=, N, N-diethylsulfamoyl group, N-(
2-dodenruoquinethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g.,
Methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group! , etc.), sulfinyl groups (e.g., octane sulfinyl n, dodenyl sulfinyl group, phenyl sulfinyl group, etc.), alkoxycarbonyl groups (e.g. tJ-1', methoxycarbonyl group, butyloquine carbonyl, dodenyl (e.g., phenyloxycarbonyl group, octanesulfonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, octanesulfonyl group, etc.),
represents a pentadecyloxy-carbonyl group (1, etc.), and X
is a hydrogen atom P, a haloan atom (e.g., chlorine atom, bromine atom, iodine atom, etc.), a carboxyl group, or a group carried by an oxygen atom (e.g., acetoquine, probanoyloxy group, benzoyloxy group, l-dichloropenzoyluoquine group, ethoquinoxaloyloxy group, pyruvinylzugishi group, cinnamoyluoquine group, phenoxy 7 group,
Goon anophenoxy group, l-methanesulfonamidophenoxy group, goon methanesulfonylphenoxy group, α-
naphthoquine group, 3-pentadecylphenoquine group, benzyloxyluponyloquine group, ethoxy group, tucyanoethoxy group, benzyloxy group, 2phenethyloquine group, 2phenoquinethoquine group, j-phenyltetrazolyloxy group, two-penzothiazolyloxy group, etc.),
Groups connected via nitrogen atoms (side light, benzenesulfonamide group, N-ethyltoluenesulfonamide group, hetutafluoroptanamide group, -213eSt+'+'-pentafluorobenzamide group, octanesulfonamide I
J=, p-cyanophenylureido group, N,N-diethylsulfamoylamino group, l-pyboridyl group,! ,
! -dimethyl-2. l-dioxo-3-oxazolidinyl group, /-benzyl-ethquin-3-hydantoynyl group, 2N-i, i-dioxo-J(,2)1>-oxo-
l, two-benzointhiazolyl group, two-oxol l, kojihydro-l-pyridinyl group, imidazolyl group, pyrazolyl group, 3,! -diethyl,2,9-triazol-/-yl,! - or 6-promobenzotriazol-7-yl,! -Methyl-/l+2.3. Dartriazol-l-yl group, benozimidazolyl group, 3-
hair'/ru-l-hydantoinyl group, /-benzyl-terhexadecyloxy-3-hydantoinyl group,
j-methyl-7-tetrazolyl group, V-methoquinophenylazo group, goupivaloylaminophenylazo group, dihydroxy-couprobanoylphenylazo group, etc.),
Groups linked via a sulfur atom (e.g., phenylthio, 2
-Rikiru fkin phenylthiom (, two metkin! -1
-octylphenylthio i, g-methanesulfonylphenylthio active, l-octane sulfonamide 2-enylthio active, two-butoxyphenylthio group, 2-(2-hecyphensulfonylethyl) -j-ter to -octylphenyl Thio group, benzylthio exhaustion, cone anoethylthiooxygen, l~ethquinyltridenylthio group,!
- Phenylru 2.3. g.

j-tetrazolylthio group, -1penzothiazolylthio group, 2-F denorthionethiophenylthio group, 2-phenyl-3-dodenyl-1.29% t-triazolyl-j-thio group, etc.).

When R1, R2, 几3 or Yl becomes a divalent group to form a bis body, this 2g5 group is further added to 1; more specifically, a substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group) , /, 10-gunlen group, -(,:
H2CH2-0-CH2C)12-1 etc.), substitution or device (east phenylene group (e.g.

/, ni-phenylene l=, /, 3-phenylene group, -he 1-4CO-It-(:0N)i-group (1 represents a substituted or unsubstituted alkylene group or phenylene group).

When the compound represented by the general formulas [■] to [■] is present in a vinyl monomer, the linking group represented by R1, R2 or R3 is an alkylene group (substituted or unsubstituted alkylene group, for example, Methylene group, ethylene group, l, 10-denlene, -C1l□C1 (2oCH2UH2-1, etc.)
, phenylL'7i (Im or indeterminate) unilene group, such as /, ni-phenylene group, /, 3-phenylene group, (:1-13 -NH(,:0-1-<: oNH-+-0-1-OCO
- and aralkylene groups (e.g., α, etc.).

In addition, the vinyl group in the vinyl monomer has the general formula [11]
It also includes cases in which it has substituents other than those represented by ~[■]. Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having /-g 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-phthylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylic acid, etc.) Acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate.

t-butyl acrylate, 1so-butyl acrylate, -1-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroquine 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 (L-vinyltoluene, cyhinylbenzene, vinylacetophenone and sulfostyrene), itacone-resistant Turmeric powder, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g., vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N-vinyl-hydrolide/, N-vinylpyridine, and vinylidene chloride. There is 7%= of YoO goovinyl viridi.Here, the non-brother color ↑′L edge/swimming unsaturated monolayer is more than 2-L.
This also includes cases where it is used in conjunction with a request.

From [■] above [■! Examples of compounds and synthesis methods of couplers represented by the general formulas up to [2] have been described in the following literature. , E1. ,l:j,.

The compound of general formula (11) is disclosed in JP-A No. 59-162548.
etc., the compound of general formula (nl) is disclosed in JP-A-60-436
59 etc., the compound of general formula (IV) is
27411 etc., the compound of general formula (V) is disclosed in JP-A-59
-17195G and patent application No. 59-27745, etc.-
The compound of formula (Vl) is disclosed in JP-A-60-33552, etc., and the compound of general formula [■] is disclosed in U.S. Patent No. 3.0 [3].
1,432, etc., respectively.

Also, JP-A-58-42045, JP-A-59-21485
4, 59-177553, 59-177554, and 59-177557, etc., are applicable to any of the compounds of -f general formulas [■] to [■]. Ru.

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

(8f-/) CH3 (M-21 Fi3 BVI-j) (M-4n (M-r) n-CIO) 121 (M-go) (Hei 2) +M-/) (M-91 2a5 ( M-/O) n-UlOk'121 (M-//) (M-/x) c ~ I-/j) (M-1w) (M-/j) cH3n-C6H13 (M-/bu) ( M-/7) (%1-//) n-C6H13 (M-/ri) (~l-10) (Nl-,!/) (M-22) (Nl--23) (M-coV ) α しH3 (M--2rl (hi-2Otsu) (M-27) c song” (1) (M-=
! ) Day 0 3 (M-29) Low Cl0H21 (M-30 n (-1082l 1M-321 (Pvl-33) (1 mouse ratio, same below) (M-jg) x:y=yo:t.

(81-jjl -ta 3) I Nl -s da) C8H17't) (~1-r ot) (M-j7) (M-r♂) C8H17(t) (M-!ri) (M-to) These couplers is generally from 2 x 10-3 moles to jxlo' moles per mole of silver in the emulsion layer, preferably /X/02%. X/0
'Mole is added.

Two or more of the above couplers and the like can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or even the same compound! Of course, there is no problem in adding it to different 2jΦ or more.

To introduce the coupler into the silver halide hole layer C, a known method may be used, such as the method described in US SGF Patent Application No. 32, No. 022. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphorus esters (diphenyl phosphate, triphenyl phosphate, docresyl 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. dibutquine ethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimenoate), etc., or boiling point Approximately 3Q0C to l
! QOC agents such as lower alkyl acetate such as ethyl acetate, butyl acetate, propionized ethyl, 2
Butyl alcohol, methyl isobutyl ketone, β-ethyne ethyl acetate, methyl cellosolve acetate, etc. are dissolved in I'-16 and then dispersed in an aqueous colloid. The above-mentioned polyhydric solvent and low boiling point organic solvent may be used in combination.

Next, the color version 1 used in non-invention! ! Liquid (I will explain using two).

The color mixture used in the present invention does not substantially contain benzyl alcohol. “Substantially not containing” means
Preferably l! The benzyl alcohol concentration is 3 or less in me/i, more preferably 0, rme/i or less, and most preferably no benzyl alcohol is contained at all.

The color developer used in the invention contains a known aromatic amine color developing agent. Preferred examples are p-phenylenediamine derivatives, and one representative example is shown below, but the invention is not limited thereto.

D-/N, N-diethyl-p-phenylenediamine D-22-amino-j-diethylaminotoluene D-J Koamino-5-(N-ethyl-N-laurylamino)toluene D-g 9-[h-ethyl-N -(β-hydroquinethyl)aminocoaniline D-32-methyl- to -CN-ethyl-N-(β-hydroquinethyl)aminocoaniline D-,! K N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-l-aminoaniline D-7N-<2-amino-! -diethylaminophenylethyl) methanesulfonamide D-/N, N-dimethyl-p-phenylenediamine D-ta guamino-3-methyl--dithylhemethoxyethylaniline [)-10u-amino-3-methyl-- Ethyl N-
1-Ethoxyethylaniline p-11g-amino-3-methyl-h-ethyl-β
-butoxy7ethylaniline These p-phenylenediamine fatty conductors are also valuable acids, hydrochlorides, sulfites, p-1 luenesulfone i! j! It may also be salt such as salt. The aromatic-grade amine is used at a concentration of about 0.1 g, more preferably from about 9 to about 10 g, per 12 hours of urine solution.

The color developer used in the present invention may contain various hydroquine lamino compounds as a preservative.

Although hydroquinyl aminos can be used in the free amine form in color developers, they are more commonly used in the form of water-soluble acid salts. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, and carbonates.

Acetate and others. Hydroquinylaminos may be substituted or unsubstituted, and the nitrogen atom of hydroquinylaminos may be substituted with an alkyl group.

The cooling l of hydroquine lamine is 0 per 72 color developer.
1 to 10f is preferred, and even more preferably 0 to 51. Color current 13! As long as the stability of the liquid is maintained, and also from the viewpoint of fogging, it is preferable that the amount added be small.

In addition, as a preservative, it may contain sulfites such as sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, and potassium memetite, and carbonyl sulfite adducts. preferable. The amount of these added is preferably Q2 to 20f/1, more preferably 01 to jP7.8, and as long as the stability of the color developer is maintained, a small amount is preferable.

11 and 1, respectively, by Haku Kimamata, 11th and 1st, respectively - JP-A No. 5 Niida 9♂ko♂, same evening Otsu-'1703/, same J4-3211. t
No. o, j 9- / j Q /g No. 2 and US Patent 32, aromatic polyhydroquine compound described in No. 4jKK, US Patent 3, No. 16503 and British Watch / 30≦/7
Hydroquinacetones described in No. 6, JP-A-Sho! Co/H3
α-aminocarbonyl compounds described in No. O20 and No. 12!, JP-A-57-5t da/%, No. f and No. 7-j J 7-9, etc. various TFMs described in JP-A No. 62-102727, hydroxamic acids described in JJ-27.4i3♂,
α described in Tatar 76Q7%t1.

α′-dicarbonyl compound, same j? -1!06F! salicylic acids described in the same No. jK-3632, poly(alkylene imines) described in the same jj-9KjSt No. 2, gluconic acid derivatives described in the same No. 2! I can give it to you. Two or more of these preservatives may be used as required.

The color development layer used in the present invention preferably has a pH
9-12, more preferably 9-//, Q1), the color developer may contain other known developers fl i'ffl
It can contain ingredients (compounds).

In order to maintain the above pH, it is preferable to use various buffering agents.

Buffers include carbonates, phosphates, borates, tetraborates, hydroquine benzoates, guanine salts, N-dimethylglycine salts, loin salts, norloin salts, guanine salts, 3. goodihydroxyphenylalanine salt, alanine salt, aminobutyrate, -mono-amino-2-methyl-/,
3-propanediol salt, valine salt, proline salt, trishydrone aminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroquine benzoates have high solubility and pH values of 9 and 0 or higher).
It is particularly preferable to use these buffering agents because of the following advantages: (1) they have excellent buffering ability in the I region, have no adverse effect on photographic performance (fogging, etc.) even when added to color developing solutions, and are inexpensive.

Specific examples of these buffering agents include IJium carbonate, potassium carbonate, sodium bicarbonate, potassium carbonate,
Trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroquine benzoate (salicylic acid) Sodium), potassium 0-hydroxybenzoate,!
= sulfohydroquine benzoin sodium sodium ter-sulfosalicylate),! Potassium r-sulfosalicylate (r-potassium sulfosalicylate) and the like can be mentioned. However, the present invention is not limited to these 11 compounds.

It is preferable that the amount of addition to the color standard f', i of the loose "grI[1] is 0.7 mol/or more, particularly 0.
．． 7 moles/! ˜0, Damor/Yari is particularly preferred.

In addition, various chelating agents can be used in the color development phase as calcium and magnesium precipitation prevention agents or to improve the stability of the color developer.

As the chelating agent, organic acids (preferably arsenic compounds are used; for example, Japanese Patent Publication No. Shogu ♂-030gu 9≦ and Japanese Patent Publication No. 1 Gu 30232)
Aminopolycarboxylic acids described in JP-A No. 1, No. 1, No. 1, No. 1, No. 1, No.
'47, special public Shoj Otsu-39359 and West German clock 22
Organic phosphonic acids described in No. 22 and No. 39, JP-A-ShojJ-1
027λ≦ issue, j3-92730 issue, same! Lee l co l
/22, No. 66-/2 Otsu No. 2+11, No. 95 No. 95 of the same, etc., and other JP-A-Sho! ♂-/95♂l! No., same Ta♂-203ZlO and special public Akira! Compounds described in No. 3-lθ900 and the like can be used. Specific examples are shown below, but the invention is not limited to these.

・ Nitrilotriacetic acid ・ Diethylenetriaminepentaacetic acid ・ Triethylenetetraminehexaacetic acid ・ N,N,N-)rimethylenephosphonic acid ・ Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid ・ / , 3-diamino- 2-Propanol-9 Vinegar
Trans-chlorohexanediaminetetraacetic acid, nitrilotripropionic acid, l,2-diaminopropanetetraacetic acid, hydroquinethyliminodiacetic acid, glycol ether diaminetetraacetic acid, hydroquineethylenediaminetriacetic acid, ethylenediamine orthohydroquinphenylacetic acid, J-phosphonobutane -/, 2. ni-)! J carboxylic acid /-hydroquinethane-/, /-diphosphonic acid/N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid Two or more of these chelating agents may be used as necessary. It's okay to use them together.

The amount of these chelating agents added may be sufficient to sequester all the ions in the color developer. For example /-
0 per e. /9-10g.

Various development accelerators can be added to the color developer of the present invention. As a development accelerator, Japanese Patent Publication No. 32-7
Otsu or, r issue, 37-j9♂7, 3/-2♂26
No. 1 Rule t<t-/, No. 23rO, Solidity 5-9θ No. 9 and US Patent No. 3. Thioether compounds described in ♂13, 2da No. 2, etc.; JP-A No. 2-9♂29, and the same! 0-
p-Fuynylenediamine compound described in /63ri No. 9; JP-A-1996 Q-/J 272≦ No., JP-A-Sho 1 Gu 3
002 f issue, JP-A-Sho jt-/j≦♂2 issue and same, f2
-13 Grade ammonium salts described in U.S. Pat. No. 10,122 and U.S. Pat.ノ/9゜tl A
p-amine phenols described in No. 2; US Pat.
9K, No. 903, 3. /2F, No. 112, u,
No. 230.79≦, No. 3,213,919, Tokuko Sho /-//'73/, U.S. Pat.

l/ko, tag wo issue, same ko, j9 otsu, wa 2 otsu issue and same 3.
Octopus, amine compounds described in No. 39 Otsu, etc.;
2-/gore No. 2-/gore No. 2-207, U.S. Patent 3
1ko♂l♂No.3, Tokuko Akira/-11931, '12
-23Jrr3 and U.S. Patent J, j32, jQ1
Polyalkylene oxides described in No. 1, etc., l-phenyl-3-pyrazolidones, hydrazines, menion type compounds, thione type compounds, imidazoles, etc. can be added as necessary. Particularly preferred are thioether compounds and l-phenyl-3-pyrazolidone systems.

In the present invention, the color developer contains KXlo-3r.
Contains no.13/-e or less bromine ions. As long as fog does not occur, it is currently 15! From the viewpoint of promotion, it is preferable that the six forces oJn be as small as possible, preferably θ~3×
lOn10τ/-e. In addition, Nanoya KC1! is an inorganic antifoggant. It is preferable to add a compound that provides chloride ions such as. It is also preferable to add various organic antifoggants as necessary. Specific examples are shown below, but are limited to these.

H3 CH3 CH3 CH3 0 days.

C3to1□ 2H5 goose -C3H7 IS 0-C5Hll CH3 0 days.

CH3 shi1-i3 n-c 3rd day 7 n-C31 (7 l-13 OL'1-13 H2 5H UH3(,:H3 OOH OOH 03Na CH2CH2NH2 CH20H2COOH Co-nc 5)+,.

It is preferable that the amount of these antifoggants added be as small as possible as long as fogging is prevented, and 0 per color developing layer 72 is preferable.
．． 07 to 7.01 is preferred, more preferably 0.0
/~0.21.

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

The color development fft of the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent 11, K,1-diamino-,2,u'-disulfostilbene compounds are preferred. Preferably, the value is 0-rf/J3, and more preferably o, ig to +1/1.

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

The processing temperature of the color development layer of the present invention is preferably 20 to 1/OOC, more preferably 30 to I/O'(,').The color development time is preferably 20 seconds to 2 minutes, and even more preferably 30 seconds to ) minutes. Here, "color development time" refers to the time from the time when the photosensitive + dye material comes into contact with the color developer solution until it comes into contact with the processing solution of the next bath, and also includes the so-called transfer time. be.

The amount of replenishment is preferably 2020-600 ml per liter of light-sensitive material, and more preferably 0 to 300 ml per liter of photosensitive material.

Particularly preferably 700m6 to 200me.

In the present invention, a bleach-fixing process is performed after color development. The shorter the bleach-fixing time, the better, 7 minutes 30 minutes.
It is less than seconds, particularly preferably less than 7 minutes. Here, “
"Bleach-fixing time" is also the time from when the photosensitive material comes into contact with the bleach-fixing solution to when it comes into contact with the washing water of the next bath.
'+' is the time spent immersed in the fixing bath plus the transit time, ie the residence time in the air.

The bleach-fix solution of the present invention contains sulfites (e.g., ammonium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium bisulfite, sodium bisulfite), potassium bisulfite, etc. as preservatives. , etc.), metabisulfites (e.g. potassium metabisulfite,
Sodium metabisulfite, ammonium metabisulfite,
Contains sulfite ion-releasing compounds such as ↑. These compounds are approximately 0,0/-0,! in terms of sulfite ions.
It is preferable to contain 0 mol/-8, and more preferably 0 mol/-8.
There is.

Other preservatives that can be used in the present invention include hydroxylamine, hydrazine, and bisulfite adducts of aldehyde compounds (eg, acetaldehyde bisulfite).

The bleaching agent used in the bleaching bath of the present invention is iron (1
) organic complex salts (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid,
Complex salts such as aminopolyphosphonic acid, phosphonocarphonic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; and hydrogen peroxide. Among these, organic complex salts of iron ([l) are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Iron (I
Aminopolycarboxylic acids, aminopolyphosphonic acids, organic phosphonic acids, or their salts useful for forming organic complex salts of II) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β -Oquinethyl)-N,N
', N'-triacetic acid.

/, 2-diaminopropanetetraacetic acid.

Triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, chlorohexanediaminetetraacetic acid, /, 3-diamino-2-panoltetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxylaminoniacetic acid Acetic acid, Dihydroquine ethyl ether diamine tetraacetic acid, Glycol ether diamine tetraacetic acid, Ethylene diamine tetrapropionic acid, Ethylene diamine nibropionic acid.

phenylenediaminetetraacetic acid, 2-phosphonobutane-7. Co, 9-triacetic acid, /, 3-diaminopropanol-, N, N'.

N'-tetramethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid.

/,3-propylenediamine-N,N,N',N'-tetramethylenephosphonic acid.

Examples include l-hydroquinethylidene-/, /-monodiphosphonic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron CI [l,3-diaminopro-ξ-tetraacetic acid, methyliminodiacetic acid]
) Complex salts are preferred because they have a high bleaching edge.

1 of these bleaches per bleach-fixer no. 0.0 for expediting purposes. /j~0. j mole is preferred, more preferably 08-! ~o, V mol.

The fixing agent used in the bleach-fix solution of the present invention is a known fixing agent, namely, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thioanate; ethylene bisthioglycolic acid. , 3゜≦-dithia/, J'-octanediol and other water-bathable halogen monoarsenic solubilizers such as thioureas (1).
Can be used by mixing 11 pieces of ``a'/kashi or 2 sticks''. In addition, a special bleaching constant S=, which is made of a combination of a fixing agent and a large amount of a monohypotassium iodine dichloride halide, etc., as described in JP-A-5R-IRS3RQ, can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

Bleach-fixing '15/The amount of fixing agent per A is 0.3
The range is preferably 2 mols, more preferably 0 mols.

The p)l region of the bleach-fix solution in the present invention is preferably y-, and more preferably j to 7.5.

If p1-1 is lower than this temperature, the desilvering performance will be improved, but the deterioration of the grain and the leuco of the cyan dye will be accelerated.On the other hand, if the pH is higher than this, the desilvering will be delayed and the staining will be delayed. It is more likely to occur.

pH 1 tone 1! i For C2, add hydrochloric acid depending on the required C2,
Sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash,
Caustic soda, sodium carbonate, potassium carbonate, etc. can be added.

In addition, the bleaching constant S solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Further, a bleach accelerator may be used in the bleach-fixing solution, if necessary. Examples of useful bleach accelerators include:
U.S. Patent No. J, 793 J! No. ♂, West German patents 1 and 2
90. ♂No.12, @32. Oj9゜err No., JP-A-63-. Same issue as 327J! No. 3-67731, No. 32
Dano No., same j3-≦5732, same Ta! -7'262
No. 3, same r 3-9 j & No. 30, same! 3-9563
No. 1, No. 3-1041232, No. 1! 3-7 O02 da, same 53-/ni/niko 3, same! 3-2♂12≦ issue,
Research Disclosure
Disclosure) No. 71617129 (197♂
Compounds containing a mercapto group or a disulfide group as described in JP-A No. 2003-111000-11.0/29 C
Described thiazolidine derivatives; Tokkosho<1!
r-760 Otsu No., Japanese Patent Publication No. JF2-20732, same r3
-322J evening issue, US Patent No. 3.20≦,! Thiourea derivatives described in No. 61 C2; West German Patent No. 1,/27.71
No. j, Iodide described in Japanese Patent Application Publication No. Shoj♂-7≦23j; West German Patent No. 9≦Otsu9%tlQ, same j,? 9t♂.

Polyethylene oxides described in No. U30;
! - Polyamine f-hypolymer compound described in No. 3 of JP-A No. 3; and other JP-A No. 2-g, No. 31, No. 9-! 944tK No., j3-tag No. 922, jK-3!7,! Issue 7, same evening! -2! Examples thereof include the compounds described in No. 06 and JR-7 No. 399tO, as well as iodine and bromine ions.

Among these, compounds that have a mercapto group or a disulfide group are preferred from the viewpoint of having a large promoting effect, and are particularly preferred in US Patent > s3. trq3, ♂j♂, West German patent no. i, 2t)o
, No. 212, and JP-A No. 3-96-30 are preferred.

In addition, the bleach constant S=-2 of the present invention is a bromide (e.g. potassium bromide, ammonium bromide, ammonium bromide)
or chlorides (e.g. potassium chloride, sodium chloride,
(ammonium chloride) or iodides (eg ammonium iodine) can be used. Boric acid, borax, sodium meta hard shell, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, as required
Addition of 7 or more types of inorganic acids such as tartaric acid having a 91-1 buffering capacity of 100, organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine, or fluorescent brighteners. Can be done.

The processing temperature of this bleach-fixing process is ioQ~! 0 DEG C. (: is preferable, and 200 DEG C. to 0 DEG C. is more preferable. Also, the supplementary light amount is preferably RIme to .ltoreq.oome per photosensitive material Bm, and more preferably 301 to 200 ml.

After the bleach-fixing step, water washing and/or stabilization treatment is performed. Various compounds can be used in the water washing and stabilization steps in the present invention for various purposes. For example, it is known to add bactericidal agents and anti-inflammatory agents to prevent the growth of various bacteria, molds, and algae. For example, Journal of Antibacterial and Antifungal Agents (J.
cL.

Antifung, Agents) vol, / /
, ybs.

Compounds described in pages 202 to 223 (/?♂3) and compounds described in Hiroshi Horiguchi's ``Chemistry of Antibacterial and Antibacterial Indicators''), or JP-A No. 7-rj'13, JP-A No. 52-! ♂／
r, t3, JP-A-77-97630, JP-A-Shoyu♂-10
j/%t! , JP-A Showa ♂-1371636° JP-A-69
-9/'4740, JP-A-J9-/26!33, JP-A-Shotaq-//71351g, JP-A-59-/! 533≦,
JP-A-30-2397 TAQ, JP-A-T 0-23976
/, Japanese Patent Application Publication No. 1973-. 2 to 72 to l, JP-A-Sho≦θ-24
09j2, Japanese Patent Application Publication i+8. t/-a1%t9, JP-A-6 Norco♂9 to 7, JP-A, 4/-, 2/9Kj, JP-A 5
The compounds and methods for using the same described in the specification of Japanese Patent Application No. 9-7 TA'17J and Japanese Patent Application No. 6 O-IOR"IZA 2 can be applied.

In particular, 1-inchazolone derivatives (2-octyl-l-inchazolin-3-one, j-chloro-methyl-l-
isothiazolin-3-one, etc.), one sulfanilamide derivative (sulfanilamide, etc.), and benzotriazole N4 form (benzotriazole, yo-methyl-
Benzotriazole! -chlorobenzothiazole, etc.) are useful. It is known that various chelating agents are added for the purpose of improving the image stability + , Unexamined Japanese Patent Publication Showa J7-
J'f Da No. 3, JP-A Showj 7-/97-ri No. 20, JP-A Showj
♂-1%t♂3q, JP-A-5! -/3, Otsu No. 36, JP-A Showa J9-/2≦S33, JP-A Showa 9-1F'13w
No. 3, JP-A-59-l♂u3 and No. 1, JP-A-Sho! 9-7
3'l to the man! R issue, JP-A-1999-/Jr-633-bu, JP-A-40-/3J-9'12, JP-A-60-23 Otsu!
No. 32, JP-A No. 60-2397'lr, JP-A-Shobu 0-
2397g9 No., JP-A Sho-Otsu Q-2392-0, JP-A Sho-O-K3RI 2-Ta No. 1, Mochi-Kai Sho-30-2'12'L Ta!
No., JP-A-60-2 Otsu-761, JP-A-Sho,! ! ,/−
107.17, Tokukai Sho 1-voso, Tokukai Sho/
-¥0! No. 1, Tokukai Shoutsu l-g Q! Ko No. 1) 1 Sho Otsu / -K Oj No. 7, Tokukai Sho ni / -K Oj 71
No. 2 in JP-A No. 67-2r9.

The compound O and the method of use described in the specification of JP-A No. 2003-120010/-Co♂ Tag No. F can be applied. In particular, ethylenediaminetetraacetic acid, diethylene) IJaminepentaacetic acid.

Nitrilotriacetic acid, l-hydroquinethylidene/.

l'-diphosphonic acid and ethylenediaminetetramethylphosphonic acid are useful.

Metal compounds can also be used in combination with these chelating agents. For example, bismuth R-H compound (JP-A-Sho!; f
-/JKl? , No. 4), Ba, Ca.

Ce-Co-In-La, Mn, Ni, r'b, Ti
, Sn-Zn, Zr compounds (Tokkai An!2-/fu3'
1'7), Mg, AI, Sr compounds (Japanese Patent Application Laid-open No. 1986-
/♂! 336) etc., special ζmi B i, C: a, Mg
-AI compounds are useful.

Furthermore, in order to effectively wash with water, a surfactant may be used (JP-A-57-/9';
Form # A method of contacting with an ion exchange resin for the purpose of removing the impurities (Japanese Unexamined Patent Publication No. 2003-02203)
, How to dispose of Hira-sho (Unexamined Japanese Patent Publication No. 60-2-2/Q! No. 3)
, activated carbon, clay materials, polyamide-based polymer compounds, polyurethane-based polymer f-hybrid compounds, phenol production January effect, epochino tree effect, polymer compounds containing hydrazide, polymers containing polytetrafluoroethylene (hiaimono, 7
or polyhydric alcohol methacrylic acid monoester-polyhydric alcohol methacrylic acid monoester-polyhydric alcohol methacrylic acid polyester copolymer: (Japanese Patent Publication No. 2003-20000-2 Otsu-3i3i), method of electrodialysis treatment (Japanese Patent Publication No. &/-21'9 da No. 9) etc. can be applied.

Furthermore, ultraviolet irradiation and magnetic field penetration methods can also be applied as methods for preventing the growth of bacteria and mold.

Furthermore, when processing continues, 0-23
3 Otsu! No. 7, Doro 1.0-23r/No. 33, Doro 0-26
39tlt No. 1, same(,/-(70th issue, same 6/-"
70shi No. 9, same /-ri 0! ! No., same Otsu/-L1tOri No.6, same≦/-t,t Q Tough No., same 6/-90ri♂
No. 930 can be applied.

In the water washing and stabilizing bath 1, in addition to the above-mentioned scratching agent, a fluorescent whitening agent, hardening agent, etc. may be added.

In addition, various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sub-1a fff, and ammonium thiosulfate are added as membrane pFI adjustment agents after treatment. I
Is it preserved? It is preferable for improving T.

As for the various additives, two or more of the same or different desired compounds may be used in combination depending on the purpose.

The amount added should be reduced to the minimum required to achieve the purpose.
V is desirable from the viewpoint of the physical properties of the emulsion film (stickiness, etc.) of the photographic material after processing.

The water washing or stabilization process is carried out in a multi-stage counter-current process using a column or more.
It is preferable that the amount of compensation is as low as possible. The amount of light supplementing liquid is 0 compared to the amount of prebath brought in per unit area of YSS material.
, 1.10 times more preferably C2, preferably 3 to 30 times
It's double.

The water washing or stabilization treatment temperature of the present invention is 20 to 5°C.
C is preferable, more preferably 25°C to u00c:, particularly preferably 30 to 3! It is OC.

This processing time is preferably less than μ minutes, more preferably,
It is preferably shorter than 2 minutes.

In order to enhance the effect of washing out the components in the film during washing with water or feminization treatment, it is preferable to perform circulatory agitation on the face.
In particular, a method (for example, gas stirring, temporary spraying, etc.) that draws individual streams on the surface of the photosensitive material is preferable.

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

The halogenated emulsion used in the present invention is silver chlorobromide or silver chloride, which does not substantially contain silver iodide.

The silver halide preferably used is silver chlorobromide having a composition in which the content of silver chloride is Omolar or more.

The term "substantially free of silver iodide" as used herein means that the content of H1-grown silver iodide is 1 mol or less, and preferably does not contain any slag. Father, the chlorobromide sulfur used in the present invention preferably has a silver chloride content! It has a composition of 0 molar width or more, and more preferably a composition of 60 molar width or more.

In order to obtain an emulsion with sufficient sensitivity without increasing fog, it is preferable that the silver chloride content be ♂O mol or less, but if particularly quickness is required, it may be 10 mol or more or 1 f 90 mol. It may be preferable to use more than 100%. Reducing the silver bromide content not only improves the speed of development, but also improves the equilibrium determined by the relationship between replenishment g and t in the developing solution when a photosensitive material containing it is run in a processing solution. Since the accumulated bromine ions exist at a low concentration, Lm (@) is preferable because the rapid developability of the solution itself can be set high.

The silver chlorobromide color photographic light-sensitive material of the present invention can be composed of 41 layers of photosensitive silver halide holes of -Jfm or more, and at least one of these two or more photosensitive silver halide emulsion layers is A silver halide emulsion layer containing silver chlorobromide grains having a silver chloride content t of 50 moles or more is preferable. Other photosensitive silver halide emulsions 1fII
There are no particular restrictions on the composition of silver halide, but silver chlorobromide grains containing at least 30 molar amount of silver chloride,
Or chlorobromide (preferably made by rolling arsenic grains with gold), and the silver bromide and arsenic (■) in the silver chlorobromide color photographic light-sensitive material are all... % or less, preferably less than about 10 mol%.

The halogen-1 arsenic grains used in the present invention may have different phases inside and on the surface, may have a multi-phase structure such as a bonded structure, or may consist of a uniform phase throughout. good. Also, they may be (・konpressed).

Used for non-invention - [Ruha Rogun (Higin 11 children's average TV
, child size (for spherical or nearly solid particles, the particle diameter is the principal r, and for cubic particles, the principal r is the child size, and the projected area (average based on the two) is 2μ.
Below is 0. /μ or more is preferred, and particularly preferred is lμ or less 0. /jμ or more. The particle size distribution may be narrow or wide.

halo y7 (hi ηU !i'L agent particle size variation standard deviation value overall average f7 j direct (variation rate n is within !0%, T'su (2'lf) [preferably within 15 hiro] So-called li-dispersed silver halide emulsion emulsion l Y is preferably used in the present invention.Also, in order for the light-sensitive material to satisfy the target gradation level, it must have substantially the same color sensitivity. Monodisperse silver halide emulsions of 2a or more with different grain sizes (preferably those having the above-mentioned fluctuation rate as monodispersity) are mixed in the same layer or in separate layers. Furthermore, two or more types of polydisperse silver chloride emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or used in combination.

The shape of the logonized plane particles used in the present invention is cubic, with regular (re
Q) may also have a gular crystalline structure.

Irregular, such as spherical
It may have a specific crystal form, or it may have a composite form of these crystal forms. Also, tabular grains may be used,
In particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly ♂ or more, account for 50% or more of the total projected area of the rL grains. It may be an emulsion consisting of a mixture of these various crystal forms.1゜These various emulsions may be either a surface latent image type in which a latent image is formed on the surface as a king, or an internal latent image type in which a latent image is formed inside one grain. .

The photographic emulsion used in the invention is described by Grafkides [Chemistry and Physics of Photography J (:P, Q!afkides).

Uhimie et Physique Photog
raphique (published by 1'aul Mantel, 19≦7)], by Duffin [Photographic Emulsion Chemistry J [:
(J, F, L) uffinV biholographic
Emulsion Chemistry (l'oc
al Press /946)], Zelikman et al., “Photo! Production and Coating of PL Agents J [V, L.

Making an by Zelikman et 31
oating Potographic Emu
lsin (published by Focal Press /9fK)
It can be prepared using the method described in ]. In other words, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting soluble silver salt and soluble α-gen salt include one-sided mixing method, simultaneous mixing method, and combinations thereof. Either of these may be used. It is also possible to use a method in which particles are formed under zero limited ion overburden (so-called reverse l-concentration method).

pkg of silver halide in the liquid phase produced as a form of simultaneous mixing method? It is also possible to use a constant control method, the so-called co/trolled 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.

Furthermore, an emulsion prepared by a conversion method including a process of converting the silver halide already formed in C1 to a more soluble, conventionally small silver halide until the silver halide grain formation process is completed; Emulsions which have been subjected to similar halogen modification after the completion of the silver oxide grain formation process can also be used.

In the process of forming halogen-1 arsenic grains or physically ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may coexist.

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

Known halogenation &! @ilF+1 (for example, ammonia, Rodankali or U.S. Special Review No. 3, 27/, /yo 2, JP-A-Shoyu/-/ 2 J 40, JP-A-Sho 53-/
,! ', tor, JP-A-Sho J3-/¥Kj-79, JP-A-5K 1007/7 or JP-A-Show tK-/! !
The thioether compounds and thione compounds described in No. 2, etc.) can be used in precipitation, physical ripening, and chemical ripening.

To remove soluble silver salts from the emulsion after physical ripening,
Nudel water washing, flocculene sedimentation method, ultraleak 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, thiobalates, thioureas, and mercapto compounds).

sulfur sensitization method using reducing substances (e.g., dichloromethane salts, amines, dorazine derivatives, formamidine sulfinic acid, Nran II compounds); metal compounds (e.g. , total complex salts, Pt, I
A noble metal sensitization method using complex salts of metals in group Vllll of the periodic table such as r, Pd, Rli, and Fe can be used alone or in combination.

The evening-sensitive, green-sensitive and red-sensitive emulsions of the present invention are each spectrally sensitized with a methine dye or the like so as to have color sensitivity. The dyes used include 77′ dyne dye,
Melonanine pigment, composite cyanine pigment, composite melonanine pigment, holobolanine pigment, heminoamine pigment, styryl pigment.

and hemioquinonol dyes. Particularly useful dyes are those belonging to the n-anine dyes, melon-anine dyes and complex melon-anine dyes.

For these dyes, any of the basic chaste ring nuclei commonly used for anine dyes can be used. Namely, pyrroline nucleus and oxazoline nucleus.

Thiazoline nucleus - virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and: an aromatic element in these nuclei Nuclei in which carbon and arsenic are fused; namely, indolenine cedar, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole cedar, benzothiazole cedar, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus , quinolino nuclei, etc. can be used. These nuclei may be placed on carbon atoms.

Melonanine dyes or complex merocyanine dyes have a ketomethylene structure as the core, pyrazolin-5-one, thiohydanodoin, 2-thioxazolidine-2.
, ni-dione nucleus, thiazolidine-21%1-dione tilt, rhodanine cedar, chi, t-valbinol acid nucleus, etc.! ~6
Members can apply different types of nuclear weapons.

These sensitizing dyes may be used individually, but combinations thereof! Combinations of sensitizing dyes are often used, especially for supersensitization purposes. Typical examples are U.S. Patent No. 2.6♂♂, J.S. No. 5, and the same! .

977.229, same j, 397.0≦θ, same 3,
jko2. Ota No. 2, J, j27, th1, No. 3
．． t/7, 293, J, 62/, 96e, 3.
≦≦B, IlO, 3. ≦72. ? No. 9♂, same 3. Otsu 79,'! , No. 2r, J, 703.

No. 327, No. 3.2≦9,301, No. 3. ♂/l, 3
No. 09 - 3. ♂32. ♂t2, same 9゜02g, 20
No. 2, British Patent 11/, 3%t%t, 2J'/No. 1, Ta 07. ! No. 03, Special Publication Showa 93-da No. 936, same!
J-/, ), J 75, JP-A-52-/10
Otsu/? 106 F2.

Along with the sensitizing dye, it is a dye that does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
It may also be included in a photochromic agent that exhibits supersensitization.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast group or being polymerized. Coupling active position is hydrogen atom)
1 equivalent substituted with a leaving group than a 4 equivalent color coupler
With color couplers, the amount of coated silver can be reduced. Suitable color pigment 1! Couplers that affect their diffusivity, colorless couplers, or DI couplers or gap promoters that release development inhibitors with the coupling reaction? Emitting couplers can also be used in one change.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Pat.
107, No. 210, No. λ, ? No. 2j, 067 and No. 3, 26 of the same, so≦ issue, etc. are described in C2.
In the present invention J2, it is preferable to use a double duty yellow coupler, and US Pat.
, KK7, No. 927, No. J, 933, No. 3Q1, and No. 02=.

Oxygen atom separation type 0) yellow coupler described in No. 6-0 etc. or Special Publication Showa 5 f-/0”/J
No. 9, U.S. Patent No. 1, 'ttO/, 762, U.S. Patent No. 1
．． 32 Otsu. θ; Su issue, nDi to 63 ( / q7
(January 2016).

British patent number 1 and 2! , No. 0, No. 10, West German Application Publication Condolences, 2/9, No. 9/7, No. ',. 2+/, J Otsu 7
No., same No. 2, J'+29, Evening? No. 2 Omahi No. 1'
tt33. A representative example of this is the nitrogen atom separation type yellow coupler described in No. 1, etc.

The α-pivaloylacetanilide thread coupler has poor color fastness, especially C two-light fastness, and the -1000α-benzoylacetanilide coupler provides high color density.

Examples of magenta couplers that can be used in the present invention include oil-protected indacylon or cyanacetyl couplers, preferably pyrazoloazole couplers such as j-pyrazolones and pyrazolotriazoles. The yarn coupler is preferably a coupler substituted with an arylamino group or an acylamino group at the 3-position from the viewpoint of the hue and coloring density of the coloring dye, and representative examples thereof include U.S. Pat. Ko.

3da No. 3,703, same No. 2. Do, No. 7/♂, No. 2.907.573, No. 3,062. Otsu! No. 3, same No. 3. / Octopus, No. 296 and iJ.

93≦, No. 075, etc. Two equivalents Os-
As a leaving group for pyrazolone couplers, U.S. Pat.
, 310. Preferred are the nitrogen atom leaving groups described in US Pat. No. 33/797 or the arylthio groups described in US Pat. Also, European Patent No. 23. It has a ballast group as described in No. 3 B! - Pyrazolone couplers provide high color density.

As the pyrazoloazole coupler, the general formula (
Particularly preferred are those shown in 1).

Cyan couplers that can be used in the present invention with τ divalents include oil-protected naphthol-based and phenol-based couplers 1), US Pat. No. 1, 7K.

The naphthol-based cuffler described in No. 293, preferably U.S. Pat.
No. 6, No. DA, No. 22r, No. 233 and No. '1, 29 of the same.
A representative example is the oxygen atom dissociating type two-equivalent naphthol coupler described in No. 4,200. Further, specific examples of phenolic couplers are given in US Patent No. 2. J, g9
, 9j No. 9, No. ko, ♂0/, No. 171, No. 2,
772, /≦No. 2, same No. 2. It is described in ♂9j, ♂2g issues, etc. Cyan couplers that are robust to humidity and temperature It are preferably used in the present invention, and a typical example thereof is the one described in U.S. Pat. Alkyl group! Phenolic yarn cyan coupler with ears, U.S. Patent Nos. 772,162, 3.75♂, 30♂, U.S. Pat. No. K, 327.

/23rd, West German Patent Publication No. 3,329,729 and Special Request Akira! f-, the U, turn-amino substituted phenolic couplers described in US Pat. LILI Otsu, Go No. 2, Do No. Da, 333.9
99ぢ, I5J th v, tri, evening! These include phenolic couplers having a phenylureido group '&W at the J-position and an acylamino group at the J-position, which are described in No. 9 and No. 127,767.

Granularity can be improved by using a coupler that moderately diffuses the coloring dye. This kind of pigment diffusive power fuller is the first grade of rice painting, J Otsu ≦.

,! Specific examples of magenta couplers are found in British Patent No. 32 and British Patent No. 2,12, No. 570, and European Patent No. 9.4.1.
No. 70 and West German Application Publication No. 53. r3w.

No. 533 describes specific examples of yellow, magenta or cyan couplers.

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. 31. ♂2
No. 0 and the same No. G, Q♂0゜, No. 2//. Specific examples of polymerized magenta couplers include British Patent No. 1,102,123 and U.S. Pat.
347,-'! No. f2 is marked i [(5).

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer, or in combination in the same compound in order to satisfy the characteristics required for the photosensitive material f1. It is also possible to enter two or more different types.

The coupler used in the present invention can be prepared using an oil-in-water dispersion method (which can be placed in a barrel into the photosensitive material 1). After dissolving either one of the so-called auxiliary solvents alone or a mixture of the two, they are finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant.An example of a high boiling point organic solvent is disclosed in US Pat. , 32, No. 027, etc. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, etc. It may be applied by divalent coating.

Specific examples of high boiling point organic 8 agents include phthalic acid esters (dibutyl phthalate, dichlorohexyl phthalate, dichoethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid 9()'
J phenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, trichoethylhexyl phosphate, tridodenyl phosphate, tryptoquine ethyl phosphate, trichloropropyl phosphate, dicoethylhexyl phenyl phosphate, etc.)
, benzoic acid esters (2-ethylhexylbenzoate, dodenlebenzoate, 2-ethylhexylbenzoate, 2-ethylhexylbenzoate, 2-ethylhexylbenzoate,
hydroquine benzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.),
Alcohols or phenol M (isostearyl alcohol, 2.l-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, inostearyl lactate, trioctyl nodrate, etc.) , aniline visit book (N,N-dibutyl phthalate)
t-manritylanili 7, etc.), hydrocarbons (parafi/
, dodenlebenzene, diisopropylnaphthalene, etc.)
Examples include. In addition, as an auxiliary solvent, the boiling point is approximately 3
40'
Organic solvents of C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, coetoquine ethyl acetate, dimethylformamide, and the like.

The process and effects of the latex dispersion method and specific examples of latex for impregnation are described in U.S. Patent %t, t, /99°3 Otsu No. 3,
West German Patent Application (OLS) No. 2. ! 'II.

No. 22 and No. 2. j<t/, No. 230, etc.

The standard usage amount of the color coupler is in the range of 0.00 to 1 mole per mole of photosensitive silver halide, preferably 0,00 /2 mol for yellow coupler and 0 for magenta coupler. 0.003 to 0.3 mole, and o, oor to 0.3 mole for cyan couplers.

The photographic material produced using the present invention contains hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamides as color antifogging agents or color mixing inhibitors. Phenol d! It may contain 9 bodies, etc.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
O-hydroquine chromans, j-hydroquine coumarans, spirochromans, p-alkoxyphenols, bisphenols! Centered on hindered phenols,
Typical examples include gallic acid derivatives, methylenedioquine benzene derivatives, amine phenols, hindered amines, and ether or ester derivatives obtained by anrylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoquinamide)nickel complex and (bis-N,N-dialkyldithiocarbamad)nickel complex can also be used.

U.S. Patent No. 9.1 is used to prevent the deterioration of yellow pigment 1 due to heat, humidity, and sources. Compounds in which the fractional structures of hindered amine and hindered phenol are contained in the same molecule, as described in Niotoshi, No. 593, give good results. In addition, in order to prevent deterioration of the agenta dye gap and deterioration due to special effects, Pf Kaisho! T-/69 and the Subiroindan part listed in the issue, and Tokukai Sho! j-7973! Hydroquinoro -derived or monoethel substituted chroman focuses in the issue give a preferred result.

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

The amount of UV absorber applied should be just enough to impart photostability to the cyan dye surface, but if too much is used, it will cause a color photographic effect) and yellowing of the unexposed areas (white areas) of the material. 1 Usually preferably / >4 /
0 mol/m-2X/0-3 mol/m2,
jKlO mol/m ~/ in bamboo, ! It is set in the range of xIQ-3 mol/m2.

In the light-sensitive material layer structure of ordinary color paper, either one of the layers on either side adjacent to the cyan coupler-containing red-sensitive emulsion pot,
Preferably, both layers contain an ultraviolet absorber.

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 light-sensitive material of the present invention may contain a water-soluble dye (1) in the hydrophilic colloid layer as a filter dye, or for various purposes such as preventing irradiation or halaying.

The photographic emulsion layer or other hydrophilic colloid layer of the photosensitive material 1 of the present invention may also contain brighteners such as stilbenone, triazine, oxazole, or coumarin. A bathing thing! Water-insoluble brighteners may also be used in the form of dispersions.

As mentioned above, the present invention can be applied to a multilayer multicolor photographic material (1) having at least two different spectral sensitivities on a support. The layer has at least one emulsion layer, and one blue-sensitive emulsion.The order of these layers can be arbitrarily selected according to the requirements, for example, a red-sensitive emulsion layer, a green-sensitive emulsion layer, a blue-sensitive emulsion layer, It can be applied to sensitive breasts and viscera.

Furthermore, each of the above-mentioned emulsions may be made up of two or more emulsion layers with different sensitivities, and even if an insensitive layer exists between λ or more emulsion layers with the same sensitivity. good.

In the photosensitive material 1-1 according to the present invention, in addition to the silver halide emulsion layer, it is preferable that appropriate auxiliary layers such as a protective layer, an intermediate layer, a filter 1, a halide prevention layer, and a hack 1 layer are provided.

As a bonding bank or protective colloid that can be used for one row of holes or the intermediate Iω,
Seratin? Q) or Akari is used, but other hydrophilic colloids can also be used.

Examples include seratin conductor, graft polymers of gelatin and other polymers, protein trade such as albumin and casein;
Hydroquine ethylcellulose, calhoginomethylcellulose, cellulose acid esters, sugar derivatives such as alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal 1, t?1J-N - Vinylpyrrolidone, polyacrylic acid.

A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Gelatin includes lime-processed gelatin, acid-processed gelatin, and ``Journal of the Japanese Society of Photographic Science J (Bull).

Snc, Sci, Photo, Japan, )/16/
Enzyme-treated gelatin as described in page 4.30 (/96≦) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In addition to the above-mentioned additives, the forestry material to which the present invention applies may include.

In addition, various stabilizers, anti-staining agents, developing agents or their precursors, development accelerators or precursors, building blocks, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other agents useful in photographic materials. An additional edition may be added.

Representative examples of these additives are Research Disclosure/2. <
g3 (72/92r) and same/, f7/Otsu (19
29////2013).

Invention 1: 1゛Reflective support that can be used for convenience is reflective! The coloring matter solid formed in the silver halide emulsion layer (2) is made clearer by increasing the color density of the silver halide emulsion layer (2).Such reflective supports include titanium oxide, lead oxide, calcium carbonate, calcium sulfate, etc. on the support. Light-reflecting materials! These include those coated with a hydrophobic resin that contains a dispersed material, and those that use a hydrophobic resin as a support to disperse an original reflective material.For example, baryta paper, polyethylene-coated paper, and polypropylene thread. Synthetic paper, transparent supports with reflective materials or reflective materials, such as glass plates, polyester films such as polyethylene terephthalate, cellulose nitrate, cellulose nitrate, polyamide films, polycarbonate films, polystyrene films, etc. These supports can be appropriately selected depending on the purpose of use.

[Example 1] A multilayer color photographic paper having the layer structure shown in Table A on top of a paper support laminated on both sides with polyethylene was prepared. The coating solution was prepared as follows.

First layer coating solution prepared Yellow coupler (a) /2, /2 and color image stabilizer (b)
), ethyl acetate core, 2 ml and solvent (C) 7
, 9 me'f was added and dissolved in the bath, and the dissolved α was 10% sodium dodecylbenzenesulfonate! It was emulsified and dispersed in IO% gelatin aqueous solution izrme containing me. -Silver bromide emulsion (Silver bromide J' OmoE, A g 70 P/
ky Gold-containing (2) Blue-sensitive sensitizing dye shown below
/mo, 7.0 x 10' mQl per g was added to make a blue-sensitive emulsion (dust) 5909p4. The emulsified dispersion and the emulsion are mixed and dissolved so that the composition shown in Table A is obtained.
The temperature was adjusted to prepare a first layer coating solution. 2nd WJ~7th
The layer coated powder was also prepared in the same manner as the 117 layer coated powder.

Various gelatin hardening agents include -l-oxy-3,5-
dichloro-5-triazinna) IJium salt was used.

The following spectral sensitizers were used in each emulsion.

Blue sensitive emulsion layer (7 per halogenated jm/moA, OX/0-
'mo13 addition) Green-sensitive emulsion L'so5o38N (L:zHs)3 (haoy71Jmz mo,,ea'J g,oX
/ o'mo-e6. Ig) SO3HN ((-2
H5) 3 (halogenated Kr/per mo-g 7.oxlo
mo-6Si added) red-sensitive emulsion layer C2H3Ie(-'2H5 (silver halide 1 mo, e per 1, oxlo m
o-8 addition) The following dyes were used as irradiation prevention dyes in each emulsion layer.

Green-sensitive emulsion layer: S O3K S O3K Red-sensitive emulsion layer: The structural formulas of the compounds used in this example, such as couplers, are as follows.

(a) Yellow coupler l-13 (b) Color image stabilizer (C) Solvent (d) Oto1 (e) Magenta coupler U8H,7 (t) ('') Color image stabilizer (g) Solvent 2 2/Mixture (weight ratio) (i) Color mixing inhibitor H (J) Solvent (ISO 91-1180 dimension P=0) After the multilayer color photographic paper obtained as described above, the following treatment is performed. Processed in the process.

Processing process Temperature Time Color development
3 IC lamp seconds, 1 minute, 3 minutes 30 seconds bleach fixing 3rC<
Wash with water for 6 seconds, dry at 36C/min for 30 seconds
The components of each treatment solution used for 1 minute of iOC are as follows.

Color Doi [Tama 7r Risui]
z00me diethylenetriaminopentaacetic acid 2. O
f Benzyl alcohol Table 7 Diethylene glycol Table 1 Sodium sulfite /,! φ Hydroquinolamine sulfate 1.01 Potassium carbonate
3jfN-methyl-N-(β-methane
Da! ? Sulfonamide ethyl)-3 Monomethyl-V-aminoaniline sulfate Fluorescent brightener (K, l-diami/, OP nostilbene series) Potassium bromide 1 Add surface water 100θmtKO) (at
pH 10,20 bleaching constant liquid water DA00rnl ammonium thiosulfate /sO
me (70%) Sodium sulfite //1 Ethylenediaminetetraacetic acid (■1)! evening? Add ammonium ethylenediaminetetraacetic acid 5g water lθooomep)i
The minimum density (Dmin) and maximum density (DmaX) of the green color of the photographic paper treated with T, 7 were measured using a Macbeth densitometer C2, and the results are shown in Table 1.

In the comparative example in Table 1, in the treatment containing benzyl alcohol (waste/, 3.6.7, /, 9),
Currently, an increase in capri is observed as time increases. Also, benzyl alcohol! When the bromide ion concentration is high (4i K, j) in the treatment without the bromine ion, color development is poor at short color development times.

By the way, in the present invention, the development time is 2 minutes or less, the power increase of Capri is small, and the color development is excellent (2 excellent).

It has excellent performance especially when the silver chloride content is ≦θ% to ♂O% (12, /3, /zo, 16-lbu, /7)
.

Furthermore, the effect of the present invention is remarkable when the degree of bromide ion is less than r, 1 x 10 mol/l. This becomes clear when comparing Dmin and Dmax with A6/l and 12.

[Example 2] The following magenta couplers (0), (P), (Q)-(R)v were used instead of the magenta coupler (e) in Example 1, and the magenta Dmin of
and Dmax were measured. The results are shown in Table 2.

co) (Sonou I/gr+ 'feat 1to, 3
s2 /rty c t * ) (R) Exemplary Compound M-57 According to Table IJ2, the increase in fog was particularly large in the treatment containing benzyl alcohol in the comparative example, whereas in the present invention, the increase in fog was particularly large. The color development time is less than 1 minute, there is almost no increase in fog, and the color development is excellent. Especially when using Virazoloaso/recoupler as magenta coupler (1630-3/, 31,
3) is particularly excellent in both fogging and color development.

[Example 3] Instead of the processing steps in Example 1, the color photographic paper of Example 1 was processed in the following processing steps.

Processing process Temperature Time Color development 3jC Zoj seconds bleaching Sadahiko 3sC vr rinse■ 3IC 20 seconds rinse■ 3jC 20 seconds rinse■ 3jC 20 seconds rinse■ 3YC 30 seconds rinse Agriculture is rinse■→■→Q→■ A countercurrent pilot was used. The compositions of the color developer and bleach-fix solution used were the same as in Example 1.

Moreover, the composition of the rinsing liquid is as follows.

(Rinse solution) /-Hydroxyethylidene-'+ /. ttmel
'-Diphosphonic acid (O%) Ethylenediamine-~, N, N', 0,
Ta1-'-tetramethylenephosphonate bismuth chloride 0.3! ? Polyvinyl biarydone 0.2! f ammonia water (
26%) 2.5 gonitrilotriacetic acid/3N3
/,OfEDTA-Kl-1
0. Evening 1 Sulfanilamide
100m9 Sodium sulfite
1.01benzotriazole
O. Ta? ! -Chloro2-methyl-K-
j O m9inch azolin-3-one λ-octyl-l-inchazo 50m9phosphorus-3-one fluorescent brightener (K, tt'-diamino i,oy
Stilbene type) Water Y7) Dete 1000me
Potash hydroxide pH 7. ! Example 1
When Dmin and Dmax were measured in the same manner as in Example 1, l×t o
A color developing layer containing less than 3 mol/m of potassium bromide and no benzyl alcohol (showed poor photographic performance upon second processing).

Below'Fi#11 [Example 4] As described in Table C, the first layer (bottom layer) to the seventh layer (
Sample 44 was prepared by coating the uppermost layer).

The coating liquid for the first layer was prepared as follows. That is, 200 g of yellow coupler shown in Table 8, 93.3 g of antifading agent, high boiling point solvent (p! 10 g and (ql
5 g and 600 mj of ethyl acetate as a co-solvent!
Alkanol B
(Alkylnaphthalene sulfonate, manufactured by DuPont)
5% water? 8't (gelatin water solution 2 containing 1330mp
(i3300m6 and emulsified using a colloid mill to prepare coupler dispersion L.) Ethyl acetate was distilled off under reduced pressure from this dispersion, and the sensitizing dye for the blue-sensitive emulsion layer and 1 -Methyl-2-mercapto-5-
1400 g of emulsion containing A7≠Luamino1.3.4-triazole (96.7 g as Ag, 17 g of gelatin)
0g) and further add 10% gelatin aqueous solution 26
00g was added to prepare a coating liquid.

The coating liquids for the second to seventh layers were prepared in the same manner as for the first layer.

The following materials were used as sensitizing dyes for each emulsion layer.

Front window emulsion layer; anhydro-5-methoxy-5'-methyl-3,3'-disulfopropyl selenacyanine hydroxide green-sensitive emulsion layer; anhydro-9-ethyl-5°51-diphenyl-3-3'-dis Rufoethyl oxacarpocyanine hydroxy red angry emulsion layer i3,3'-diethyl-5-methquine-9
, 9'-(2,2-dimethyl-1,3-propano)thiadicarpocyanine iodide.The following substances were also used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-acetylamino-1
, 3,4-triazole and the following were used as anti-irradiation dyes.

4-(3-carboxy-5-hydroxy-4-(J-(
J-Carboxy-yo-okine/-(U-sulfonatophenyl)-2-pyrazoline-ylidene-/-pro-ylidene-/-pyrazolyl)benzenesulfonate-di-
Potassium salt N, N'-(≠,!-dihydroxy?.

10-dioquino-3,7-cissulfonatoanthracene-7,! -diyl)bis(amine methanesulfonate)-
Tetrasodium salt or as a hardening agent 1. Corbis(vinylsulfonyl)ethane was used.

The couplers used are as follows.

Yellow coupler α Cyan coupler C-/c5H11 The multilayer color photographic paper obtained as above was used in Example 3.
It was treated in the same treatment steps as (-).However, the recipe for each treatment used is as follows.

Color developer triethanolamine r, ot Benzyl alcohol Table 3 N, N-diethylhydroxyamine 'A,, 29 Fluorescent brightener (≠, Hiro'-diaminostilbene series) J, or ethylenediaminetetraacetic acid m t , op potassium carbonate
30.0? sodium chloride
/,≠? ≠-amino-3-methyl-N-
Ethyl-N-(β-(methanesulfonamido)ethyl) -p-phenylenediamine sulfate j,09 Potassium bromide Table 3 pHyo, or Bleach-fix solution EDTAFe(III) NH Ko-2H20tOfEDT
A-coNa-jHuOgr Ammonium thiosulfate (70%) /λ0ytl Sodium sulfite /6f Glacial acetic acid
Add 7f water
1000yu11))T
z, r Rinse liquid EDTA@JNa-uHHO20, u? add water
Table 3 shows the results of measuring Dmin and Dmax at pH 7.0.

From the results shown in Table 3, when the -KBr concentration is higher than the range of the present invention, the coloring properties are significantly reduced (3t to 3g);
Furthermore, even if the -KBr concentration is within the range of the present invention, the presence of benzyl alcohol causes significant fogging.

Example of the present invention! The halogenated complex emulsion (1) used in Example 1 was prepared as follows.

(/liquid) (coliquid) Sulfur! (/N) ko0tttl(
3 liquid) The following silver halide solvent (i%) 3 ml H3 H3 (Hori liquid) (J liquid) (6 liquid) (7 liquid) (/liquid) was heated to 7!0C and - (2 liquid) and (3 liquid) were heated. liquid) was added. Thereafter, (≠liquid) and (liquid J) were added simultaneously for 60 minutes. Another 70 minutes later.

(Liquid 2) and (Liquid 7) were added simultaneously over a period of 2 t.

Addition! The diameter was lowered and desalted. Add water and dispersed gelagoon and adjust -pi (to t, -, average particle size 7
．． 02 μm, coefficient of variation (standard deviation divided by average particle size; s/d l 09Of.

A monodisperse cubic silver chlorobromide emulsion of #1 mole bromide was obtained. This emulsion was sensitized with gold and sulfur. As for the money.

1, θX10 mol 1 mol Ag was added, and chemical sensitization was carried out with 17 um of thiosulfate.

Next, silver halide emulsion (2) was prepared as follows.

(liquid) (9 liquids) Sulfuric acid (IN) Cog m1 (10 liquids) (coliquid) silver halide solvent (/ti) 3 pts (t
(liquid) (/liquid) (/liquid) (/liquid) (liquid Iiu) (liquid R) was heated to rt'c, and (liquid) and C10 liquid) were added. Thereafter, -(//liquid) and (/coliquid) were added simultaneously over 10 minutes. After another 70 minutes, (liquid 13) and (liquid 4) were added simultaneously over r minutes. After 3 minutes of addition, the temperature was lowered and the mixture was desalted. Add water and dispersed gelatin;
Adjust the pH to 6.2 and the average particle size O0≠! μm,
Coefficient of variation o, or, silver bromide 0. A monodispersed cubic silver chlorobromide emulsion of JMorti was obtained. Add chloroauric acid to this emulsion, l×1
0 mol 1 mol Ag was added and single gold sensitization was carried out in the same manner as (//liquid) and (13'Ft, while changing the composition and temperature of I to obtain an average particle size O1 of 7 μm with a coefficient of variation of 0.07.
A monodisperse cubic silver chlorobromide emulsion containing 1 mol of silver bromide was obtained, and this emulsion was sensitized with gold and sulfur to form an emulsion (4'4fc in 31,
The gold was optimally chemically sensitized using 4t, /×10'moles 1mol Ag added, +1um of thiosulfate.

[Example]

Multilayer color photographic papers of j0 Kirinari shown in Table C with different magenta couplers were prepared on paper supports laminated on both sides with polyethylene. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (a) 79.7g and color image stabilizer (b)
) 4t, 4tgI/c ethyl sulfate, 27. 2 ml and solvent (c)7. ．． Add and dissolve 9 ml, and add this solution to 70 ml.
-Sodium dodecylbenzenesulfonate! A 10-fiber gelatin aqueous solution containing mlf/1rfrrl was emulsified and dispersed at 1%. On the other hand, silver bromide emulsion (silver bromide 7.

mo1%, containing A g 70 E/kg) VC shown below! A blue-sensitive emulsion was prepared in an amount of 0 g by adding silver chlorobromide/mo Jl Todoroki Shita and 0×10 4rnol of the sensitivity sensitizing dye. Mix and dissolve the emulsified dispersion and emulsion, Table B
A first layer coating solution was prepared by adjusting the gelatin concentration so as to have the following composition.

The coating solutions for the first 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,! -dichloros-) riazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

-m: Sakugo m- Actually, ■ Emulsion layer (halogenated 97mol11"J) island oxio-4mol
Addition) Green-sensitive emulsion layer (silver halide 7moil@p 41.0×/0-4
mail addition) (halogenated record/rno1doro p7.oxio=5mol
Addition) Red-sensitive emulsion 1 (Silver halide/T:nol”j4p □, q ×7
04m01 addition) The following dyes were used as anti-irradiation dyes in each emulsion layer.

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

(a) Yellow coupler (b) Color image stabilizer (C) Solvent (d) Color mixing inhibitor (e) Solvent (f) Color image stabilizer (g) Solvent (h) Ultraviolet absorber (i) Color mixing Inhibitor N
) Solvent 0.2:l mixture (weight ratio) Medium (iso CgHlgO-)rP=0 The color photographic paper obtained as above was treated in the same treatment steps and treatment liquid as in Example 1.

However, the color conversion time was changed as shown in Table 1.

The measurement results of Dmin and Dmax of the obtained magenta dye are shown in Table 1.

From the results shown in Table V, when KBr is higher than the present invention, the color development is insufficient (B≠g, ≠9, !0) -KB
It can be seen that even if r is within the range of the present invention, fogging occurs relatively frequently when benzyl alcohol is present.

(Simmered j/-jJ, 13-!j, 71 t7)-Furthermore, in the present invention, if the development time exceeds 2 minutes, it is not preferable because a relatively large amount of fogging occurs.

(Effects of the Invention) By implementing the present invention, benzyl alcohol can be substantially eliminated, thereby significantly reducing the pollution load.

The liquid preparation work is reduced, and the decrease in concentration caused by cyan dye remaining in the leuco form can be eliminated. Furthermore, it is possible to rapidly process a large amount of color prints and dramatically improve productivity.

Further, according to the present invention, even if processing is carried out for a short time using a color developing solution that does not substantially contain benzyl alcohol, it is possible to obtain a good color image with little decrease in color density and low fog.

Patent applicant: Fuji Photo Film Co., Ltd. 2, Name of the invention: Processing method for silver halide color photographic light-sensitive materials 3, Person making the amendment Relationship to the case Patent applicant: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Order for amendment Date Voluntary5. Submit the description 6 of the subject of the amendment, and the engraving of the description of the contents of the amendment (no changes to the contents) 7) L-4.

1. Display of the incident Showa J/year patent application No. 12r7'l
. No. 2, Name of the invention Processing method for silver halide color photographic light-sensitive materials 3, Relationship with the case of the person making the amendment Patent applicant Address: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment "Explanation" Column 56 The description in the "Detailed Description of the Invention" section of the Description of Contents of the Amendment is amended as follows.

/) On page ≠ 3, insert "The use of substituted hydroxylamines is particularly preferred in terms of improving color development." after "may be." in the line.

2) No. ≠ 7th line on page 3 "Hydroxylami/" "Hydroxylamines" and correct it.

3) ``May be adopted.'' on the th << +@i r line [may be used in combination. Particularly preferred is the addition of aromatic polyhydroxy compounds and alkanolamines. Correct this.

≠) Insert ``ethylenediami/tetraacetic acid'' after ``triethylenetetraminehexaacetic acid'' on page ≠7/line.

rith r! page! row After “sodium bisulfite)” ``Ascorbic acid'' Insert.

6) rt page! row "/, j-j [i, 3-J and correct it.

7) Tata page/4th line After "Average and Arare Ding." Insert "Tabular grains are also expressed in terms of spheres."

Ir) 1st one! page (d) rsecJ Both rtertJ and correct it.

P) on page 121(b) [-CCH=H2J “-CCH=CHz J and correct it.

io) Page 14c3 Yellow Kabra's '-5OzNH(CH2)ao J 'kr -NH
Correct as CO(CH2) s O-J.

//) 1j page 7 line 3 "Io" "Br0" and correct it.

that's all

Claims (3)

[Claims] (1) After imagewise exposure, a photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support is substantially free of benzyl alcohol and is 4×10^-^3
1. A method for processing a silver halide color photographic light-sensitive material, characterized in that color development is carried out in 2 minutes or less using a color developer containing bromine ions in an amount of mol/l or less. (2) The silver halide color photographic light-sensitive material described above has at least one silver chlorobromide silver halide emulsion layer containing substantially no silver iodide and containing 50 mol% or more of silver chloride. The method for processing a silver halide color photographic material according to claim 1, wherein the material is a photographic material. (3) The silver halide color photographic light-sensitive material according to claim 1, characterized in that the silver halide color photographic light-sensitive material contains a magenta coupler of the following general formula (I). Processing method. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Rb represents a hydrogen atom or a substituent, and Y_1 can be separated by a coupling reaction with an oxidized aromatic primary amine developer Za, Zb, or Zc represents a methine group, a substituted methine group, =N- or -NH-, and one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. )